A Selection Rule for Hydrofluoroether Electrolyte Cosolvent: Establishing a Linear Free‐Energy Relationship in Lithium–Sulfur Batteries

Su, Chi‐Cheung; He, Meinan; Amine, Rachid; Amine, Khalil

doi:10.1002/ange.201904240

A Selection Rule for Hydrofluoroether Electrolyte Cosolvent: Establishing a Linear Free‐Energy Relationship in Lithium–Sulfur Batteries

Journal Article · Thu Jun 27 00:00:00 EDT 2019 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201904240· OSTI ID:1560181

Su, Chi‐Cheung ^[1]; He, Meinan ^[1]; Amine, Rachid ^[2]; ^[3]

Chemical Sciences and Engineering Division Argonne National Laboratory 9700 S. Cass Avenue Lemont IL 60439 USA
Materials Science Division Argonne National Laboratory 9700 S. Cass Avenue Lemont IL 60439 USA
Chemical Sciences and Engineering Division Argonne National Laboratory 9700 S. Cass Avenue Lemont IL 60439 USA, Materials Science and Engineering Stanford University Stanford CA 94305 USA

Abstract

Hydrofluoroethers (HFEs) have been adopted widely as electrolyte cosolvents for battery systems because of their unique low solvating behavior. The electrolyte is currently utilized in lithium‐ion, lithium–sulfur, lithium–air, and sodium‐ion batteries. By evaluating the relative solvating power of different HFEs with distinct structural features, and considering the shuttle factor displayed by electrolytes that employ HFE cosolvents, we have established the quantitative structure–activity relationship between the organic structure and the electrochemical performance of the HFEs. Moreover, we have established the linear free‐energy relationship between the structural properties of the electrolyte cosolvents and the polysulfide shuttle effect in lithium–sulfur batteries. These findings provide valuable mechanistic insight into the polysulfide shuttle effect in lithium–sulfur batteries, and are instructive when it comes to selecting the most suitable HFE electrolyte cosolvent for different battery systems.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1560181

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 31 Vol. 131; ISSN 0044-8249

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

Country of Publication:: Germany

Language:: English

References (44)

Development and Challenges of Functional Electrolytes for High-Performance Lithium-Sulfur Batteries Wang, Lili; Ye, Yusheng; Chen, Nan Advanced Functional Materials, Vol. 28, Issue 38 https://doi.org/10.1002/adfm.201800919	journal	July 2018
Ultrasound Assisted Design of Sulfur/Carbon Cathodes with Partially Fluorinated Ether Electrolytes for Highly Efficient Li/S Batteries Weng, Wei; Pol, Vilas G.; Amine, Khalil Advanced Materials, Vol. 25, Issue 11 https://doi.org/10.1002/adma.201204051	journal	January 2013
High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes Chen, Shuru; Zheng, Jianming; Mei, Donghai Advanced Materials, Vol. 30, Issue 21 https://doi.org/10.1002/adma.201706102	journal	March 2018
30 Years of Lithium-Ion Batteries Li, Matthew; Lu, Jun; Chen, Zhongwei Advanced Materials, Vol. 30, Issue 33 https://doi.org/10.1002/adma.201800561	journal	June 2018
Solid-State Lithium/Selenium-Sulfur Chemistry Enabled via a Robust Solid-Electrolyte Interphase Xu, Gui-Liang; Sun, Hui; Luo, Chao Advanced Energy Materials, Vol. 9, Issue 2 https://doi.org/10.1002/aenm.201802235	journal	November 2018
The Relationship between the Relative Solvating Power of Electrolytes and Shuttling Effect of Lithium Polysulfides in Lithium-Sulfur Batteries Su, Chi-Cheung; He, Meinan; Amine, Rachid Angewandte Chemie, Vol. 130, Issue 37 https://doi.org/10.1002/ange.201807367	journal	August 2018
An Intrinsic Flame‐Retardant Organic Electrolyte for Safe Lithium‐Sulfur Batteries Yang, Huijun; Guo, Cheng; Chen, Jiahang Angewandte Chemie https://doi.org/10.1002/ange.201811291	journal	December 2018
The Relationship between the Relative Solvating Power of Electrolytes and Shuttling Effect of Lithium Polysulfides in Lithium-Sulfur Batteries Su, Chi-Cheung; He, Meinan; Amine, Rachid Angewandte Chemie International Edition, Vol. 57, Issue 37 https://doi.org/10.1002/anie.201807367	journal	August 2018
An Intrinsic Flame-Retardant Organic Electrolyte for Safe Lithium-Sulfur Batteries Yang, Huijun; Guo, Cheng; Chen, Jiahang Angewandte Chemie International Edition, Vol. 58, Issue 3 https://doi.org/10.1002/anie.201811291	journal	December 2018
Aligned sulfur-coated carbon nanotubes with a polyethylene glycol barrier at one end for use as a high efficiency sulfur cathode Huang, Jia-Qi; Zhang, Qiang; Zhang, Shu-Mao Carbon, Vol. 58 https://doi.org/10.1016/j.carbon.2013.02.037	journal	July 2013
Localized High-Concentration Sulfone Electrolytes for High-Efficiency Lithium-Metal Batteries Ren, Xiaodi; Chen, Shuru; Lee, Hongkyung Chem, Vol. 4, Issue 8 https://doi.org/10.1016/j.chempr.2018.05.002	journal	August 2018
High-Efficiency Lithium Metal Batteries with Fire-Retardant Electrolytes Chen, Shuru; Zheng, Jianming; Yu, Lu Joule, Vol. 2, Issue 8 https://doi.org/10.1016/j.joule.2018.05.002	journal	August 2018
A review of electrolytes for lithium–sulphur batteries Scheers, Johan; Fantini, Sébastien; Johansson, Patrik Journal of Power Sources, Vol. 255 https://doi.org/10.1016/j.jpowsour.2014.01.023	journal	June 2014
Li-ion battery materials: present and future Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae Materials Today, Vol. 18, Issue 5 https://doi.org/10.1016/j.mattod.2014.10.040	journal	June 2015
Glyme–Sodium Bis(fluorosulfonyl)amide Complex Electrolytes for Sodium Ion Batteries Terada, Shoshi; Susa, Hiroko; Tsuzuki, Seiji The Journal of Physical Chemistry C, Vol. 122, Issue 29 https://doi.org/10.1021/acs.jpcc.8b04367	journal	July 2018
Internally Referenced DOSY-NMR: A Novel Analytical Method in Revealing the Solution Structure of Lithium-Ion Battery Electrolytes Su, Chi-Cheung; He, Meinan; Amine, Rachid The Journal of Physical Chemistry Letters, Vol. 9, Issue 13 https://doi.org/10.1021/acs.jpclett.8b01359	journal	June 2018
Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li ⁺ Solvation Structure and Li–S Battery Performance Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri ACS Applied Materials & Interfaces, Vol. 9, Issue 45 https://doi.org/10.1021/acsami.7b11566	journal	November 2017
Binary Mixtures of Highly Concentrated Tetraglyme and Hydrofluoroether as a Stable and Nonflammable Electrolyte for Li–O ₂ Batteries Zhao, Qin; Zhang, Yuhang; Sun, Guiru ACS Applied Materials & Interfaces, Vol. 10, Issue 31 https://doi.org/10.1021/acsami.8b08346	journal	July 2018
Sparingly Solvating Electrolytes for High Energy Density Lithium–Sulfur Batteries Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R. ACS Energy Letters, Vol. 1, Issue 3 https://doi.org/10.1021/acsenergylett.6b00194	journal	August 2016
Extremely Stable Sodium Metal Batteries Enabled by Localized High-Concentration Electrolytes Zheng, Jianming; Chen, Shuru; Zhao, Wengao ACS Energy Letters, Vol. 3, Issue 2 https://doi.org/10.1021/acsenergylett.7b01213	journal	January 2018
A Localized High-Concentration Electrolyte with Optimized Solvents and Lithium Difluoro(oxalate)borate Additive for Stable Lithium Metal Batteries Yu, Lu; Chen, Shuru; Lee, Hongkyung ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b00935	journal	July 2018
Bis(2,2,2-trifluoroethyl) Ether As an Electrolyte Co-solvent for Mitigating Self-Discharge in Lithium–Sulfur Batteries Gordin, Mikhail L.; Dai, Fang; Chen, Shuru ACS Applied Materials & Interfaces, Vol. 6, Issue 11 https://doi.org/10.1021/am501665s	journal	May 2014
A survey of Hammett substituent constants and resonance and field parameters Hansch, Corwin.; Leo, A.; Taft, R. W. Chemical Reviews, Vol. 91, Issue 2 https://doi.org/10.1021/cr00002a004	journal	March 1991
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives Hammett, Louis P. Journal of the American Chemical Society, Vol. 59, Issue 1 https://doi.org/10.1021/ja01280a022	journal	January 1937
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
Solvent Activity in Electrolyte Solutions Controls Electrochemical Reactions in Li-Ion and Li-Sulfur Batteries Moon, Heejoon; Mandai, Toshihiko; Tatara, Ryoichi The Journal of Physical Chemistry C, Vol. 119, Issue 8 https://doi.org/10.1021/jp5128578	journal	February 2015
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes Pang, Quan; Liang, Xiao; Kwok, Chun Yuen Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.132	journal	September 2016
Li–O₂ and Li–S batteries with high energy storage Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J. Nature Materials, Vol. 11, Issue 1, p. 19-29 https://doi.org/10.1038/nmat3191	journal	January 2012
Operando monitoring the lithium spatial distribution of lithium metal anodes Lv, Shasha; Verhallen, Tomas; Vasileiadis, Alexandros Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04394-3	journal	June 2018
Tuning the electrolyte network structure to invoke quasi-solid state sulfur conversion and suppress lithium dendrite formation in Li–S batteries Pang, Quan; Shyamsunder, Abhinandan; Narayanan, Badri Nature Energy, Vol. 3, Issue 9 https://doi.org/10.1038/s41560-018-0214-0	journal	August 2018
Unique behaviour of nonsolvents for polysulphides in lithium–sulphur batteries Cuisinier, M.; Cabelguen, P. -E.; Adams, B. D. Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C4EE00372A	journal	January 2014
Lithium–sulfur batteries—the solution is in the electrolyte, but is the electrolyte a solution? Barghamadi, Marzieh; Best, Adam S.; Bhatt, Anand I. Energy Environ. Sci., Vol. 7, Issue 12 https://doi.org/10.1039/C4EE02192D	journal	January 2014
Insight into lithium–metal anodes in lithium–sulfur batteries with a fluorinated ether electrolyte Zu, Chenxi; Azimi, Nasim; Zhang, Zhengcheng Journal of Materials Chemistry A, Vol. 3, Issue 28 https://doi.org/10.1039/C5TA03195H	journal	January 2015
Monolithic heterojunction quasi-solid-state battery electrolytes based on thermodynamically immiscible dual phases Cho, Sung-Ju; Jung, Gwan Yeong; Kim, Su Hwan Energy & Environmental Science, Vol. 12, Issue 2 https://doi.org/10.1039/C8EE01503A	journal	January 2019
Fluorinated electrolytes for 5 V lithium-ion battery chemistry Zhang, Zhengcheng; Hu, Libo; Wu, Huiming Energy & Environmental Science, Vol. 6, Issue 6 https://doi.org/10.1039/c3ee24414h	journal	January 2013
Polysulfide Shuttle Study in the Li/S Battery System Mikhaylik, Yuriy V.; Akridge, James R. Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1969-A1976 https://doi.org/10.1149/1.1806394	journal	January 2004
A Design Approach to Lithium-Ion Battery Electrolyte Based on Diluted Solvate Ionic Liquids Ueno, Kazuhide; Murai, Junichi; Moon, Heejoon Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0121701jes	journal	October 2016
Dilution of Highly Concentrated LiBF ₄ /Propylene Carbonate Electrolyte Solution with Fluoroalkyl Ethers for 5-V LiNi _0.5 Mn _1.5 O ₄ Positive Electrodes Doi, Takayuki; Shimizu, Yusuke; Hashinokuchi, Michihiro Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0611701jes	journal	January 2017
Intrinsic Shuttle Suppression in Lithium-Sulfur Batteries for Pouch Cell Application Weller, Christine; Thieme, Sören; Härtel, Paul Journal of The Electrochemical Society, Vol. 164, Issue 14 https://doi.org/10.1149/2.0981714jes	journal	January 2017
Application of Fluorine-containing Solvents to LiCoO2 Cathode in High Voltage Operation Kitagawa, Takeshi; Azuma, Kazuki; Koh, Meiten Electrochemistry, Vol. 78, Issue 5 https://doi.org/10.5796/electrochemistry.78.345	journal	January 2010

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