Understanding Solvation Behavior of the Saturated Electrolytes with Small/Wide-Angle X-ray Scattering and Raman Spectroscopy

Qian, Kun; Seifert, Soenke; Winans, Randall E.; Li, Tao

doi:10.1021/acs.energyfuels.1c03328

Understanding Solvation Behavior of the Saturated Electrolytes with Small/Wide-Angle X-ray Scattering and Raman Spectroscopy

Journal Article · Thu Nov 11 00:00:00 EST 2021 · Energy and Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.1c03328· OSTI ID:1840966

^[1]; Seifert, Soenke ^[2]; ^[2]; ^[3]

Northern Illinois Univ., DeKalb, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

Concentrated electrolytes are attracting significant attention because the solvation structures could stabilize the interface, encouraging novel electrolyte development for high-voltage and long-cycle-life batteries. Saturated electrolytes, which have the highest salt concentrations, have been rarely studied because of their shortcomings of high viscosity and low ionic conductivity. Nevertheless, the exciting solvation structure in saturated solution is still worth studying, significantly broadening the comprehensive understanding of the solvation processes. In this work, we investigate the saturated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) dissolved in seven different organic solvents, including propylene carbonate (PC), tetrahydrofuran (THF), acetonitrile (ACN), dimethylformamide (DMF), 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether (Diglyme), and tetraethylene glycol dimethyl ether (Tetraglyme). The combined small/wide-angle X-ray scattering and Raman spectroscopy are employed to study the global and local solvation structure. Here, this work demonstrates a method for detecting the structure of liquids, which will facilitate the study of structure–performance relationships and the screening of new electrolytes.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1840966

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 23 Vol. 35; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (29)

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
Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander Advanced Science, Vol. 4, Issue 8 https://doi.org/10.1002/advs.201700032	journal	March 2017
Regulating the Hidden Solvation‐Ion‐Exchange in Concentrated Electrolytes for Stable and Safe Lithium Metal Batteries Amine, Rachid; Liu, Jianzhao; Acznik, Ilona Advanced Energy Materials, Vol. 10, Issue 25 https://doi.org/10.1002/aenm.202000901	journal	June 2020
Insights into the Nanostructure, Solvation, and Dynamics of Liquid Electrolytes through Small‐Angle X‐Ray Scattering Qian, Kun; Winans, Randall E.; Li, Tao Advanced Energy Materials, Vol. 11, Issue 4 https://doi.org/10.1002/aenm.202002821	journal	December 2020
Raman spectrum of acetonitrile Neelakantan, P. Proceedings of the Indian Academy of Sciences - Section A, Vol. 60, Issue 6 https://doi.org/10.1007/BF03047422	journal	December 1964
Raman spectrum of propylene carbonate Janz, G. J.; Ambrose, J.; Coutts, J. W. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 35, Issue 2 https://doi.org/10.1016/0584-8539(79)80181-6	journal	January 1979
Decoupling the degradation factors of Ni-rich NMC/Li metal batteries using concentrated electrolytes Qian, Kun; Liu, Yuzi; Zhou, Xinwei Energy Storage Materials, Vol. 41 https://doi.org/10.1016/j.ensm.2021.06.007	journal	October 2021
Uncharted Waters: Super-Concentrated Electrolytes Borodin, Oleg; Self, Julian; Persson, Kristin A. Joule, Vol. 4, Issue 1 https://doi.org/10.1016/j.joule.2019.12.007	journal	January 2020
A structural study of LiTFSI–tetraglyme mixtures: From diluted solutions to solvated ionic liquids Aguilera, Luis; Xiong, Shizhao; Scheers, Johan Journal of Molecular Liquids, Vol. 210 https://doi.org/10.1016/j.molliq.2015.04.053	journal	October 2015
Raman spectroscopic study of solvation structure in acetonitrile/water mixtures Rowlen, Kathy L.; Harris, Joel M. Analytical Chemistry, Vol. 63, Issue 10 https://doi.org/10.1021/ac00010a006	journal	May 1991
New Concepts in Electrolytes Li, Matthew; Wang, Chunsheng; Chen, Zhongwei Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00531	journal	February 2020
Competitive Pi-Stacking and H-Bond Piling Increase Solubility of Heterocyclic Redoxmers Zhao, Yuyue; Sarnello, Erik S.; Robertson, Lily A. The Journal of Physical Chemistry B, Vol. 124, Issue 46 https://doi.org/10.1021/acs.jpcb.0c07647	journal	November 2020
Self-Assembled Solute Networks in Crowded Electrolyte Solutions and Nanoconfinement of Charged Redoxmer Molecules Shkrob, Ilya A.; Li, Tao; Sarnello, Erik The Journal of Physical Chemistry B, Vol. 124, Issue 45 https://doi.org/10.1021/acs.jpcb.0c07760	journal	October 2020
Ion Speciation and Transport Properties of LiTFSI in 1,3-Dioxolane Solutions: A Case Study for Li–S Battery Applications Raccichini, Rinaldo; Dibden, James W.; Brew, Ashley The Journal of Physical Chemistry B, Vol. 122, Issue 1 https://doi.org/10.1021/acs.jpcb.7b09614	journal	December 2017
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
Enhanced Cycling Performance of Ni-Rich Positive Electrodes (NMC) in Li-Ion Batteries by Reducing Electrolyte Free-Solvent Activity Tatara, Ryoichi; Yu, Yang; Karayaylali, Pinar ACS Applied Materials & Interfaces, Vol. 11, Issue 38 https://doi.org/10.1021/acsami.9b11942	journal	June 2019
Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes Borodin, Oleg; Suo, Liumin; Gobet, Mallory ACS Nano, Vol. 11, Issue 10 https://doi.org/10.1021/acsnano.7b05664	journal	October 2017
Tetraglyme−Li ⁺ Cation Solvate Structures: Models for Amorphous Concentrated Liquid and Polymer Electrolytes (II) Henderson, Wesley A.; Brooks, Neil R.; Young, Victor G. Chemistry of Materials, Vol. 15, Issue 24 https://doi.org/10.1021/cm034352r	journal	December 2003
Probing Transport and Microheterogeneous Solvent Structure in Acetonitrile−Water Mixtures and Reversed-Phase Chromatographic Media by NMR Quadrupole Relaxation Dawson, Erica D.; Wallen, Scott L. Journal of the American Chemical Society, Vol. 124, Issue 47 https://doi.org/10.1021/ja027226h	journal	November 2002
Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries Yamada, Yuki; Furukawa, Keizo; Sodeyama, Keitaro Journal of the American Chemical Society, Vol. 136, Issue 13, p. 5039-5046 https://doi.org/10.1021/ja412807w	journal	March 2014
Structural and Vibrational Properties of Diglyme and Longer Glymes Johansson, Patrik; Grondin, Joseph; Lassègues, Jean-Claude The Journal of Physical Chemistry A, Vol. 114, Issue 39 https://doi.org/10.1021/jp105437d	journal	October 2010
Glyme–Lithium Salt Equimolar Molten Mixtures: Concentrated Solutions or Solvate Ionic Liquids? Ueno, Kazuhide; Yoshida, Kazuki; Tsuchiya, Mizuho The Journal of Physical Chemistry B, Vol. 116, Issue 36 https://doi.org/10.1021/jp307378j	journal	August 2012
Understanding Li ⁺ –Solvent Interaction in Nonaqueous Carbonate Electrolytes with ¹⁷ O NMR Bogle, Xavier; Vazquez, Rafael; Greenbaum, Steven The Journal of Physical Chemistry Letters, Vol. 4, Issue 10 https://doi.org/10.1021/jz400661k	journal	May 2013
Concentrated electrolytes: decrypting electrolyte properties and reassessing Al corrosion mechanisms McOwen, Dennis W.; Seo, Daniel M.; Borodin, Oleg Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE42351D	journal	January 2014
Anion effects on Li ion transference number and dynamic ion correlations in glyme–Li salt equimolar mixtures Shigenobu, Keisuke; Shibata, Masayuki; Dokko, Kaoru Physical Chemistry Chemical Physics, Vol. 23, Issue 4 https://doi.org/10.1039/D0CP06381A	journal	January 2021
"Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries Suo, L.; Borodin, O.; Gao, T. Science, Vol. 350, Issue 6263 https://doi.org/10.1126/science.aab1595	journal	November 2015
Communication—Microscopic View of the Ethylene Carbonate Based Lithium-Ion Battery Electrolyte by X-ray Scattering Feng, Zhange; Sarnello, Erik; Li, Tao Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.0971816jes	journal	January 2019
From Ionic Liquids to Solvate Ionic Liquids: Challenges and Opportunities for Next Generation Battery Electrolytes Watanabe, Masayoshi; Dokko, Kaoru; Ueno, Kazuhide Bulletin of the Chemical Society of Japan, Vol. 91, Issue 11 https://doi.org/10.1246/bcsj.20180216	journal	November 2018
Microscopic Understanding of the Ionic Networks of “Water-in-Salt” Electrolytes Liu, Xinyi; Yu, Zhou; Sarnello, Erik Energy Material Advances, Vol. 2021 https://doi.org/10.34133/2021/7368420	journal	January 2021

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Understanding Solvation Behavior of the Saturated Electrolytes with Small/Wide-Angle X-ray Scattering and Raman Spectroscopy

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