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Title: Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes

Abstract

Aqueous electrolytes come with an intrinsic narrow electrochemical stability window (1.23 V). Expanding this window represents significant benefits in both fundamental science and practical battery applications. Recent break throughs made via super-concentration have resulted in >3.0 V windows, but fundamental understanding of the related mechanism is still absent. In the present work, we examined the widened window (2.55 V) of a super-concentrated (unsaturated) aqueous solution of LiNO3 through both theoretical and spectral analyses and discovered that a local structure of intimate Li+-water interaction arises at super-concentration, generating (Li+(H2O)2)n polymer-like chains to replace the ubiquitous hydrogen bonding between water molecules. Such structure is mainly responsible for the expanded electrochemical stability window. Further theoretical and experimental analyses quantitatively differentiate the contributions to this window, identifying the kinetic factor (desolvation) as the main contributor. Such molecular-level and quantitative understanding will further assist in tailor designing more effective approaches to stabilizing water electrochemically.

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1579296
Alternate Identifier(s):
OSTI ID: 1503575
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Chem
Additional Journal Information:
Journal Name: Chem Journal Volume: 4 Journal Issue: 12; Journal ID: ISSN 2451-9294
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; Aqueous electrolyte; LiNO3; aqueous solution; electrochemical stability window; molecular dynamics simulation; pair-distribution function; polymer-like chains; super-concentrated

Citation Formats

Zheng, Jiaxin, Tan, Guoyu, Shan, Peng, Liu, Tongchao, Hu, Jiangtao, Feng, Yancong, Yang, Luyi, Zhang, Mingjian, Chen, Zonghai, Lin, Yuan, Lu, Jun, Neuefeind, Joerg C., Ren, Yang, Amine, Khalil, Wang, Lin-Wang, Xu, Kang, and Pan, Feng. Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes. United States: N. p., 2018. Web. doi:10.1016/j.chempr.2018.09.004.
Zheng, Jiaxin, Tan, Guoyu, Shan, Peng, Liu, Tongchao, Hu, Jiangtao, Feng, Yancong, Yang, Luyi, Zhang, Mingjian, Chen, Zonghai, Lin, Yuan, Lu, Jun, Neuefeind, Joerg C., Ren, Yang, Amine, Khalil, Wang, Lin-Wang, Xu, Kang, & Pan, Feng. Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes. United States. doi:https://doi.org/10.1016/j.chempr.2018.09.004
Zheng, Jiaxin, Tan, Guoyu, Shan, Peng, Liu, Tongchao, Hu, Jiangtao, Feng, Yancong, Yang, Luyi, Zhang, Mingjian, Chen, Zonghai, Lin, Yuan, Lu, Jun, Neuefeind, Joerg C., Ren, Yang, Amine, Khalil, Wang, Lin-Wang, Xu, Kang, and Pan, Feng. Sat . "Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes". United States. doi:https://doi.org/10.1016/j.chempr.2018.09.004.
@article{osti_1579296,
title = {Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes},
author = {Zheng, Jiaxin and Tan, Guoyu and Shan, Peng and Liu, Tongchao and Hu, Jiangtao and Feng, Yancong and Yang, Luyi and Zhang, Mingjian and Chen, Zonghai and Lin, Yuan and Lu, Jun and Neuefeind, Joerg C. and Ren, Yang and Amine, Khalil and Wang, Lin-Wang and Xu, Kang and Pan, Feng},
abstractNote = {Aqueous electrolytes come with an intrinsic narrow electrochemical stability window (1.23 V). Expanding this window represents significant benefits in both fundamental science and practical battery applications. Recent break throughs made via super-concentration have resulted in >3.0 V windows, but fundamental understanding of the related mechanism is still absent. In the present work, we examined the widened window (2.55 V) of a super-concentrated (unsaturated) aqueous solution of LiNO3 through both theoretical and spectral analyses and discovered that a local structure of intimate Li+-water interaction arises at super-concentration, generating (Li+(H2O)2)n polymer-like chains to replace the ubiquitous hydrogen bonding between water molecules. Such structure is mainly responsible for the expanded electrochemical stability window. Further theoretical and experimental analyses quantitatively differentiate the contributions to this window, identifying the kinetic factor (desolvation) as the main contributor. Such molecular-level and quantitative understanding will further assist in tailor designing more effective approaches to stabilizing water electrochemically.},
doi = {10.1016/j.chempr.2018.09.004},
journal = {Chem},
number = 12,
volume = 4,
place = {United States},
year = {2018},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: https://doi.org/10.1016/j.chempr.2018.09.004

Citation Metrics:
Cited by: 25 works
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Figures / Tables:

Figure 1 Figure 1: (A) Illustration of the evolution of the Li+ primary solvation sheath from diluted to highly concentrated LiNO3 aqueous solution. (B-D) MD simulated local structure evolution of LiNO3 aqueous solution from concentration of 1:48 (LiNO3:H2O) to 1:2. (E) Crystal structure of LiNO3·3H2O and the (Li +(H2O)2)n polymer-like chains inmore » the crystal.« less

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