Water or Anion? Uncovering the Zn2+ Solvation Environment in Mixed Zn(TFSI)2 and LiTFSI Water-in-Salt Electrolytes

Zhang, Yong; Wan, Gang; Lewis, Nicholas C.; Mars, Julian; Bone, Sharon E.; Steinrück, Hans-Georg; Lukatskaya, Maria R.; Weadock, Nicholas J.; Bajdich, Michal; Borodin, Oleg; Tokmakoff, Andrei; Toney, Michael F.; Maginn, Edward J.

doi:10.1021/acsenergylett.1c01624

Title: Water or Anion? Uncovering the Zn²⁺ Solvation Environment in Mixed Zn(TFSI)₂ and LiTFSI Water-in-Salt Electrolytes

Journal Article · 07 September 2021 · ACS Energy Letters

DOI: https://doi.org/10.1021/acsenergylett.1c01624 · OSTI ID:1872762

^[1]; Wan, Gang ^[2];

^[3]; Mars, Julian ^[4]; Bone, Sharon E. ^[5];

^[6];

^[7]; Weadock, Nicholas J. ^[8];

^[5];

^[9];

^[10];

^[4];

^[1]

Univ. of Notre Dame, IN (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)
Univ. of Colorado, Boulder, CO (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. Paderborn (Germany)
Eidgenoessische Technische Hochschule (ETH), Zurich (Switzerland)
Univ. of Colorado, Boulder, CO (United States)
Army Research Lab., Adelphi, MD (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

Applications of aqueous zinc batteries for grid-scale energy storage are limited by their poor reversibility and the competing water splitting reaction. The recent invention of a water-in-salt (WIS) electrolyte concept provides a new route enabling a stable and highly reversible aqueous zinc battery chemistry. In the present work, a mixed zinc bis(trifluoromethane sulfonyl)imide (Zn(TFSI)₂) and LiTFSI WIS electrolyte was studied using X-ray total scattering, X-ray absorption, and Fourier transform infrared spectroscopy in conjunction with classical molecular dynamics simulations. It was found that, in the highly concentrated WIS electrolyte consisting of 1 m Zn(TFSI)₂ and 20 m LiTFSI, Zn²⁺ cations are mainly solvated by six waters in their first solvation shell, while the TFSI^– anions are completely excluded. This ion solvation picture is fundamentally different from the previous understandings. The results suggest that additional studies are needed to fully understand the unusual stability and reversibility of zinc-WIS electrolyte-based batteries.

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Research Organization:: Argonne National Laboratory (ANL), Lemont, IL (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

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

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515

OSTI ID:: 1872762

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 10 Vol. 6; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (30)

Recent Advances in Zn-Ion Batteries Song, Ming; Tan, Hua; Chao, Dongliang Advanced Functional Materials, Vol. 28, Issue 41 https://doi.org/10.1002/adfm.201802564	journal	August 2018
Recent Progress in Electrically Rechargeable Zinc–Air Batteries Fu, Jing; Liang, Ruilin; Liu, Guihua Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201805230	journal	December 2018
Recent Advances in Flexible Zinc-Based Rechargeable Batteries Li, Yingbo; Fu, Jing; Zhong, Cheng Advanced Energy Materials, Vol. 9, Issue 1 https://doi.org/10.1002/aenm.201802605	journal	November 2018
Functionalized Phosphonium Cations Enable Zinc Metal Reversibility in Aqueous Electrolytes Ma, Lin; Pollard, Travis P.; Zhang, Yong Angewandte Chemie International Edition, Vol. 60, Issue 22 https://doi.org/10.1002/anie.202017020	journal	April 2021
Influence of the Second Coordination Shell on the XANES Spectra of the Zn2+ Ion in Water and Methanol Migliorati, Valentina; Zitolo, Andrea; Chillemi, Giovanni ChemPlusChem, Vol. 77, Issue 3 https://doi.org/10.1002/cplu.201100070	journal	January 2012
The biological inorganic chemistry of zinc ions Krężel, Artur; Maret, Wolfgang Archives of Biochemistry and Biophysics, Vol. 611 https://doi.org/10.1016/j.abb.2016.04.010	journal	December 2016
Operando Visualization and Multi-scale Tomography Studies of Dendrite Formation and Dissolution in Zinc Batteries Yufit, Vladimir; Tariq, Farid; Eastwood, David S. Joule, Vol. 3, Issue 2 https://doi.org/10.1016/j.joule.2018.11.002	journal	February 2019
Crossroads in the renaissance of rechargeable aqueous zinc batteries Song, Junhua; Xu, Kang; Liu, Nian Materials Today, Vol. 45 https://doi.org/10.1016/j.mattod.2020.12.003	journal	May 2021
New Concepts in Electrolytes Li, Matthew; Wang, Chunsheng; Chen, Zhongwei Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00531	journal	February 2020
Vibrational Probe of Aqueous Electrolytes: The Field Is Not Enough Lewis, Nicholas H. C.; Iscen, Aysenur; Felts, Alanna The Journal of Physical Chemistry B, Vol. 124, Issue 32 https://doi.org/10.1021/acs.jpcb.0c05510	journal	July 2020
Water-in-Salt LiTFSI Aqueous Electrolytes. 1. Liquid Structure from Combined Molecular Dynamics Simulation and Experimental Studies Zhang, Yong; Lewis, Nicholas H. C.; Mars, Julian The Journal of Physical Chemistry B, Vol. 125, Issue 17 https://doi.org/10.1021/acs.jpcb.1c02189	journal	April 2021
Signatures of Ion Pairing and Aggregation in the Vibrational Spectroscopy of Super-Concentrated Aqueous Lithium Bistriflimide Solutions Lewis, Nicholas H. C.; Zhang, Yong; Dereka, Bogdan The Journal of Physical Chemistry C, Vol. 124, Issue 6 https://doi.org/10.1021/acs.jpcc.9b10477	journal	January 2020
Structure and dynamics of hydrated ions Ohtaki, Hitoshi.; Radnai, Tamas. Chemical Reviews, Vol. 93, Issue 3 https://doi.org/10.1021/cr00019a014	journal	May 1993
Hydrogen and Higher Shell Contributions in Zn ²⁺ , Ni ²⁺ , and Co ²⁺ Aqueous Solutions: An X-ray Absorption Fine Structure and Molecular Dynamics Study D'Angelo, Paola; Barone, Vincenzo; Chillemi, Giovanni Journal of the American Chemical Society, Vol. 124, Issue 9 https://doi.org/10.1021/ja015685x	journal	March 2002
Solvation Structure Design for Aqueous Zn Metal Batteries Cao, Longsheng; Li, Dan; Hu, Enyuan Journal of the American Chemical Society, Vol. 142, Issue 51 https://doi.org/10.1021/jacs.0c09794	journal	December 2020
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020
Realizing high zinc reversibility in rechargeable batteries Ma, Lin; Schroeder, Marshall A.; Borodin, Oleg Nature Energy, Vol. 5, Issue 10 https://doi.org/10.1038/s41560-020-0674-x	journal	August 2020
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
Recent advances in zinc–air batteries Li, Yanguang; Dai, Hongjie Chem. Soc. Rev., Vol. 43, Issue 15 https://doi.org/10.1039/C4CS00015C	journal	January 2014
A review of electrolyte materials and compositions for electrochemical supercapacitors Zhong, Cheng; Deng, Yida; Hu, Wenbin Chemical Society Reviews, Vol. 44, Issue 21 https://doi.org/10.1039/C5CS00303B	journal	January 2015
Local environment of metal ions in phthalocyanines: K-edge X-ray absorption spectra Rossi, G.; d'Acapito, F.; Amidani, L. Physical Chemistry Chemical Physics, Vol. 18, Issue 34 https://doi.org/10.1039/C6CP04022E	journal	January 2016
On the coordination of Zn ²⁺ ion in Tf ₂ N ⁻ based ionic liquids: structural and dynamic properties depending on the nature of the organic cation Sessa, Francesco; Migliorati, Valentina; Serva, Alessandra Physical Chemistry Chemical Physics, Vol. 20, Issue 4 https://doi.org/10.1039/C7CP07497B	journal	January 2018
Materials chemistry for rechargeable zinc-ion batteries Zhang, Ning; Chen, Xuyong; Yu, Meng Chemical Society Reviews, Vol. 49, Issue 13 https://doi.org/10.1039/C9CS00349E	journal	January 2020
Issues and opportunities facing aqueous zinc-ion batteries Tang, Boya; Shan, Lutong; Liang, Shuquan Energy & Environmental Science, Vol. 12, Issue 11 https://doi.org/10.1039/C9EE02526J	journal	January 2019
Challenges in the material and structural design of zinc anode towards high-performance aqueous zinc-ion batteries Du, Wencheng; Ang, Edison Huixiang; Yang, Yang Energy & Environmental Science, Vol. 13, Issue 10 https://doi.org/10.1039/D0EE02079F	journal	January 2020
Structural characterization of zinc(II) chloride in aqueous solution and in the protic ionic liquid ethyl ammonium nitrate by x-ray absorption spectroscopy D’Angelo, Paola; Zitolo, Andrea; Ceccacci, Francesca The Journal of Chemical Physics, Vol. 135, Issue 15 https://doi.org/10.1063/1.3653939	journal	October 2011
Energy storage emerging: A perspective from the Joint Center for Energy Storage Research Trahey, Lynn; Brushett, Fikile R.; Balsara, Nitash P. Proceedings of the National Academy of Sciences, Vol. 117, Issue 23 https://doi.org/10.1073/pnas.1821672117	journal	June 2020
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
"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
XAFS for Everyone Calvin, Scott https://doi.org/10.1201/b14843	book	May 2013

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