Understanding the Surprising Ionic Conductivity Maximum in Zn(TFSI)2 Water/Acetonitrile Mixture Electrolytes

Zhang, Yong; Carino, Emily; Hahn, Nathan T.; Becknell, Nigel; Mars, Julian; Han, Kee Sung; Mueller, Karl T.; Toney, Michael; Maginn, Edward J.; Tepavcevic, Sanja

doi:10.1021/acs.jpclett.3c03048

Title: Understanding the Surprising Ionic Conductivity Maximum in Zn(TFSI)₂ Water/Acetonitrile Mixture Electrolytes

Journal Article · 11 December 2023 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.3c03048 · OSTI ID:2281691

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University of Notre Dame, IN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Univ. of Colorado, Boulder, CO (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)

Aqueous electrolytes composed of 0.1 M zinc bis-(trifluoromethyl-sulfonyl)-imide (Zn-(TFSI)₂) and acetonitrile (ACN) were studied using combined experimental and simulation techniques. The electrolyte was found to be electrochemically stable when the ACN V% is higher than 74.4. In addition, it was found that the ionic conductivity of the mixed solvent electrolytes changes as a function of ACN composition, and a maximum was observed at 91.7 V% of ACN although the salt concentration is the same. This behavior was qualitatively reproduced by molecular dynamics (MD) simulations. Detailed analyses based on experiments and MD simulations show that at high ACN composition the water network existing in the high water composition solutions breaks. As a result, the screening effect of the solvent weakens and the correlation among ions increases, which causes a decrease in ionic conductivity at high ACN V%. Furthermore, this study provides a fundamental understanding of this complex mixed solvent electrolyte system.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC02-06CH11357; NA0003525; AC05-76RL01830

OSTI ID:: 2281691

Alternate ID(s):: OSTI ID: 2311271; OSTI ID: 2377139

Report Number(s):: SAND-2024-02023J; PNNL-SA-191001; 184614

Journal Information:: Journal of Physical Chemistry Letters, Vol. 14, Issue 50; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

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
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
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
Tailoring desolvation kinetics enables stable zinc metal anodes Hou, Zhen; Tan, Hong; Gao, Yao Journal of Materials Chemistry A, Vol. 8, Issue 37 https://doi.org/10.1039/D0TA06622B	journal	January 2020
Water-In-Salt LiTFSI Aqueous Electrolytes (2): Transport Properties and Li ⁺ Dynamics Based on Molecular Dynamics Simulations Zhang, Yong; Maginn, Edward J. The Journal of Physical Chemistry B, Vol. 125, Issue 48 https://doi.org/10.1021/acs.jpcb.1c07581	journal	November 2021
Ultrahigh coulombic efficiency and long-life aqueous Zn anodes enabled by electrolyte additive of acetonitrile Shi, Jinqiang; Xia, Kexin; Liu, Luojia Electrochimica Acta, Vol. 358 https://doi.org/10.1016/j.electacta.2020.136937	journal	October 2020
Confining Water in Ionic and Organic Solvents to Tune Its Adsorption and Reactivity at Electrified Interfaces Serva, Alessandra; Dubouis, Nicolas; Grimaud, Alexis Accounts of Chemical Research, Vol. 54, Issue 4 https://doi.org/10.1021/acs.accounts.0c00795	journal	February 2021
Improving Electrochemical Stability and Low‐Temperature Performance with Water/Acetonitrile Hybrid Electrolytes Chen, Jiawei; Vatamanu, Jenel; Xing, Lidan Advanced Energy Materials, Vol. 10, Issue 3 https://doi.org/10.1002/aenm.201902654	journal	November 2019
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
Strategies of regulating Zn²⁺solvation structures for dendrite-free and side reaction-suppressed zinc-ion batteries Cao, Jin; Zhang, Dongdong; Zhang, Xinyu Energy & Environmental Science, Vol. 15, Issue 2 https://doi.org/10.1039/D1EE03377H	journal	January 2022
System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers Moultos, Othonas A.; Zhang, Yong; Tsimpanogiannis, Ioannis N. The Journal of Chemical Physics, Vol. 145, Issue 7 https://doi.org/10.1063/1.4960776	journal	August 2016
Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization Tian, Yaosen; Zeng, Guobo; Rutt, Ann Chemical Reviews, Vol. 121, Issue 3 https://doi.org/10.1021/acs.chemrev.0c00767	journal	December 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
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 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
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
System-Size Dependence of Diffusion Coefficients and Viscosities from Molecular Dynamics Simulations with Periodic Boundary Conditions Yeh, In-Chul; Hummer, Gerhard The Journal of Physical Chemistry B, Vol. 108, Issue 40 https://doi.org/10.1021/jp0477147	journal	October 2004
Tuning Zn2+ coordination environment to suppress dendrite formation for high-performance Zn-ion batteries Qin, Runzhi; Wang, Yuetao; Zhang, Mingzheng Nano Energy, Vol. 80 https://doi.org/10.1016/j.nanoen.2020.105478	journal	February 2021
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
Anode for Zinc-Based Batteries: Challenges, Strategies, and Prospects Lu, Wenjing; Zhang, Changkun; Zhang, Huamin ACS Energy Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acsenergylett.1c00939	journal	July 2021
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
Metallic Zinc Anode Working at 50 and 50 mAh cm⁻² with High Depth of Discharge via Electrical Double Layer Reconstruction Shi, Xin; Wang, Jin; Yang, Fan Advanced Functional Materials, Vol. 33, Issue 7 https://doi.org/10.1002/adfm.202211917	journal	December 2022
Enhanced reversibility and electrochemical window of Zn-ion batteries with an acetonitrile/water-in-salt electrolyte Song, Xueyang; He, Huibing; Aboonasr Shiraz, Mohammad Hossein Chemical Communications, Vol. 57, Issue 10 https://doi.org/10.1039/D0CC06076C	journal	January 2021
Electrolyte Strategies toward Better Zinc-Ion Batteries Liu, Cunxin; Xie, Xuesong; Lu, Bingan ACS Energy Letters, Vol. 6, Issue 3 https://doi.org/10.1021/acsenergylett.0c02684	journal	February 2021
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
The role of the temperature in reversed-phase high-performance liquid chromatography using pyrocarbon-containing adsorbents Colin, Henri; Diez-Masa, José Carlos; Guiochon, Georges Journal of Chromatography A, Vol. 167 https://doi.org/10.1016/S0021-9673(00)91145-2	journal	December 1978
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
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
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
Energy Storage Chemistry in Aqueous Zinc Metal Batteries Wan, Fang; Zhou, Xunzhu; Lu, Yong ACS Energy Letters, Vol. 5, Issue 11 https://doi.org/10.1021/acsenergylett.0c02028	journal	October 2020
Viscosity measurements of methanol–water and acetonitrile–water mixtures at pressures up to 3500bar using a novel capillary time-of-flight viscometer Thompson, J. Will; Kaiser, Theodore J.; Jorgenson, James W. Journal of Chromatography A, Vol. 1134, Issue 1-2 https://doi.org/10.1016/j.chroma.2006.09.006	journal	November 2006
Boosting Zinc Electrode Reversibility in Aqueous Electrolytes by Using Low‐Cost Antisolvents Hao, Junnan; Yuan, Libei; Ye, Chao Angewandte Chemie International Edition, Vol. 60, Issue 13 https://doi.org/10.1002/anie.202016531	journal	February 2021
The Fate of Water at the Electrochemical Interfaces: Electrochemical Behavior of Free Water Versus Coordinating Water Dubouis, Nicolas; Serva, Alessandra; Salager, Elodie The Journal of Physical Chemistry Letters, Vol. 9, Issue 23 https://doi.org/10.1021/acs.jpclett.8b03066	journal	November 2018
New Concepts in Electrolytes Li, Matthew; Wang, Chunsheng; Chen, Zhongwei Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00531	journal	February 2020
Special Editorial Perspective: Beyond Li-Ion Battery Chemistry Whittingham, M. Stanley Chemical Reviews, Vol. 120, Issue 14 https://doi.org/10.1021/acs.chemrev.0c00438	journal	July 2020
Solid-state electrolytes for beyond lithium-ion batteries: A review Aziam, Hasna; Larhrib, Badre; Hakim, Charifa Renewable and Sustainable Energy Reviews, Vol. 167 https://doi.org/10.1016/j.rser.2022.112694	journal	October 2022
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
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

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Understanding the Surprising Ionic Conductivity Maximum in Zn(TFSI)2 Water/Acetonitrile Mixture Electrolytes

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Title: Understanding the Surprising Ionic Conductivity Maximum in Zn(TFSI)₂ Water/Acetonitrile Mixture Electrolytes