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

Journal Article · · Chem
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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.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1579296
Alternate ID(s):
OSTI ID: 1503575
Journal Information:
Chem, Journal Name: Chem Vol. 4 Journal Issue: 12; ISSN 2451-9294
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 134 works
Citation information provided by
Web of Science

Cited By (12)

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Improving Electrochemical Stability and Low‐Temperature Performance with Water/Acetonitrile Hybrid Electrolytes journal November 2019
Electrolytes for Dual‐Carbon Batteries journal March 2019
Water in Rechargeable Multivalent-Ion Batteries: An Electrochemical Pandora's Box journal January 2019
Mechanically Robust Gel Polymer Electrolyte for an Ultrastable Sodium Metal Battery journal December 2019
A 2.4-V asymmetric supercapacitor based on cation-intercalated manganese oxide nanosheets in a low-cost “water-in-salt” electrolyte journal July 2019
A Perspective: the Technical Barriers of Zn Metal Batteries journal January 2020
A promising water-in-salt electrolyte for aqueous based electrochemical energy storage cells with a wide potential window: highly concentrated HCOOK journal January 2019
A low-cost “water-in-salt” electrolyte for a 2.3 V high-rate carbon-based supercapacitor journal January 2019
Understanding the cathode electrolyte interface formation in aqueous electrolyte by scanning electrochemical microscopy journal January 2019
Benchmarking Conductivity Predictions of the Advanced Electrolyte Model (AEM) for Aqueous Systems journal October 2019

Figures / Tables (26)

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Related Subjects

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