skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes

Abstract

Electrodeposition is a widely practiced method for creating metal, colloidal, and polymer coatings on conductive substrates. In the Newtonian liquid electrolytes typically used, the process is fundamentally unstable. The underlying instabilities have been linked to failure of microcircuits, dendrite formation on battery electrodes, and overlimiting conductance in ion-selective membranes. We report that viscoelastic electrolytes composed of semidilute solutions of very high–molecular weight neutral polymers suppress these instabilities by multiple mechanisms. The voltage window ΔV in which a liquid electrolyte can operate free of electroconvective instabilities is shown to be markedly extended in viscoelastic electrolytes and is a power-law function, ΔV : η 1/4, of electrolyte viscosity, η. This power-law relation is replicated in the resistance to ion transport at liquid/solid interfaces. We discuss consequences of our observations and show that viscoelastic electrolytes enable stable electrodeposition of many metals, with the most profound effects observed for reactive metals, such as sodium and lithium. This finding is of contemporary interest for high-energy electrochemical energy storage.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Cornell Univ., Ithaca, NY (United States)
Publication Date:
Research Org.:
Cornell Univ., Ithaca, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1499929
Grant/Contract Number:  
SC0016082
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 3; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wei, Shuya, Cheng, Zhu, Nath, Pooja, Tikekar, Mukul D., Li, Gaojin, and Archer, Lynden A. Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes. United States: N. p., 2018. Web. doi:10.1126/sciadv.aao6243.
Wei, Shuya, Cheng, Zhu, Nath, Pooja, Tikekar, Mukul D., Li, Gaojin, & Archer, Lynden A. Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes. United States. doi:10.1126/sciadv.aao6243.
Wei, Shuya, Cheng, Zhu, Nath, Pooja, Tikekar, Mukul D., Li, Gaojin, and Archer, Lynden A. Fri . "Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes". United States. doi:10.1126/sciadv.aao6243. https://www.osti.gov/servlets/purl/1499929.
@article{osti_1499929,
title = {Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes},
author = {Wei, Shuya and Cheng, Zhu and Nath, Pooja and Tikekar, Mukul D. and Li, Gaojin and Archer, Lynden A.},
abstractNote = {Electrodeposition is a widely practiced method for creating metal, colloidal, and polymer coatings on conductive substrates. In the Newtonian liquid electrolytes typically used, the process is fundamentally unstable. The underlying instabilities have been linked to failure of microcircuits, dendrite formation on battery electrodes, and overlimiting conductance in ion-selective membranes. We report that viscoelastic electrolytes composed of semidilute solutions of very high–molecular weight neutral polymers suppress these instabilities by multiple mechanisms. The voltage window ΔV in which a liquid electrolyte can operate free of electroconvective instabilities is shown to be markedly extended in viscoelastic electrolytes and is a power-law function, ΔV : η1/4, of electrolyte viscosity, η. This power-law relation is replicated in the resistance to ion transport at liquid/solid interfaces. We discuss consequences of our observations and show that viscoelastic electrolytes enable stable electrodeposition of many metals, with the most profound effects observed for reactive metals, such as sodium and lithium. This finding is of contemporary interest for high-energy electrochemical energy storage.},
doi = {10.1126/sciadv.aao6243},
journal = {Science Advances},
number = 3,
volume = 4,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1. Fig. 1. : Electrochemical characteristics of the viscoelastic electrolytes. (A) I-V curves of electrolytes with different polymer concentrations. (B to D) Voltage versus time profiles measured in electrolytes with (B) no PMMA, (C) 2 wt % PMMA, and (D) 8 wt % PMMA at current densities ranging from 0.316 tomore » 2.526 mA/cm2. (E) Average tracer particle velocities measured in an optical lithium||stainless steel cell containing control (no polymer) and viscoelastic liquid electrolytes containing 4 wt % polymer. (F) Average tracer particle velocities measured in control and viscoelastic liquid electrolytes as a function of current density.« less

Save / Share:

Works referenced in this record:

The cathode–electrolyte interface in the Li-ion battery
journal, November 2004


Deionization shocks in microstructures
journal, December 2011


Effect of Turbulence on Limiting Current in Electrodialysis Cells
journal, December 1959

  • Cowan, Donald A.; Brown, Jerry H.
  • Industrial & Engineering Chemistry, Vol. 51, Issue 12
  • DOI: 10.1021/ie50600a026

Coupling between Buoyancy Forces and Electroconvective Instability near Ion-Selective Surfaces
journal, May 2016


Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries
journal, October 2015


Equilibrium electro-osmotic instability in concentration polarization at a perfectly charge-selective interface
journal, September 2017


Copper Deposition in the Presence of Polyethylene Glycol
journal, January 1998

  • Kelly, James J.
  • Journal of The Electrochemical Society, Vol. 145, Issue 10
  • DOI: 10.1149/1.1838829

Review on gel polymer electrolytes for lithium batteries
journal, January 2006


Nonflammable perfluoropolyether-based electrolytes for lithium batteries
journal, February 2014

  • Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 9
  • DOI: 10.1073/pnas.1314615111

Effect of Electrolyte Composition on Lithium Dendrite Growth
journal, January 2008

  • Crowther, Owen; West, Alan C.
  • Journal of The Electrochemical Society, Vol. 155, Issue 11
  • DOI: 10.1149/1.2969424

Electric Birefringence of Electrolytes near Charged Surfaces, II:  Effect of Polymeric Additives
journal, October 2007

  • Saha, Sourav; Archer, Lynden A.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 39
  • DOI: 10.1021/jp0700231

A stable room-temperature sodium–sulfur battery
journal, June 2016

  • Wei, Shuya; Xu, Shaomao; Agrawral, Akanksha
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11722

Formation of a mesh-like electrodeposit induced by electroconvection
journal, February 1994

  • Wang, Mu; van Enckevort, Willem J. P.; Ming, Nai-ben
  • Nature, Vol. 367, Issue 6462
  • DOI: 10.1038/367438a0

Nanocomposite polymer electrolytes for lithium batteries
journal, July 1998

  • Croce, F.; Appetecchi, G. B.; Persi, L.
  • Nature, Vol. 394, Issue 6692
  • DOI: 10.1038/28818

Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries
journal, February 2006

  • Kang, Kisuk; Shirley Meng, Ying; Breger, Julien
  • Science, Vol. 311, Issue 5763, p. 977-980
  • DOI: 10.1126/science.1122152

Electro-osmotic slip and electroconvective instability
journal, May 2007


Electrochemical aspects of the generation of ramified metallic electrodeposits
journal, December 1990


Electrical Energy Storage and Intercalation Chemistry
journal, June 1976


Role of the membrane surface in concentration polarization at ion-exchange membrane
journal, January 1988


Electrodeposition of polymer coatings
journal, July 1988


Highly Stable Sodium Batteries Enabled by Functional Ionic Polymer Membranes
journal, January 2017


Calculation of the space charge in electrodeposition from a binary electrolyte
journal, February 2006


Electric Birefringence of Electrolytes near Charged Surfaces, I
journal, October 2007

  • Saha, Sourav; Archer, Lynden A.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 39
  • DOI: 10.1021/jp0700229

Mechanics and Prediction of Turbulent Drag Reduction with Polymer Additives
journal, January 2008


Design principles for electrolytes and interfaces for stable lithium-metal batteries
journal, September 2016


Electrodeposition of composite coatings containing nanoparticles in a metal deposit
journal, September 2006


100k Cycles and Beyond: Extraordinary Cycle Stability for MnO 2 Nanowires Imparted by a Gel Electrolyte
journal, April 2016


Role of convection in thin-layer electrodeposition
journal, April 1995

  • Huth, John M.; Swinney, Harry L.; McCormick, William D.
  • Physical Review E, Vol. 51, Issue 4
  • DOI: 10.1103/PhysRevE.51.3444

Electro-osmotically induced convection at a permselective membrane
journal, August 2000


Interface layer formation in solid polymer electrolyte lithium batteries: an XPS study
journal, January 2014

  • Xu, Chao; Sun, Bing; Gustafsson, Torbjörn
  • J. Mater. Chem. A, Vol. 2, Issue 20
  • DOI: 10.1039/C4TA00214H

Field-Induced Layering of Colloidal Crystals
journal, May 1996


Transition of lithium growth mechanisms in liquid electrolytes
journal, January 2016

  • Bai, Peng; Li, Ju; Brushett, Fikile R.
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE01674J

Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions
journal, July 2016

  • Tikekar, Mukul D.; Archer, Lynden A.; Koch, Donald L.
  • Science Advances, Vol. 2, Issue 7
  • DOI: 10.1126/sciadv.1600320

An EIS Study of the Anode Li/PEO-LiTFSI of a Li Polymer Battery
journal, January 2003

  • Bouchet, R.; Lascaud, S.; Rosso, M.
  • Journal of The Electrochemical Society, Vol. 150, Issue 10
  • DOI: 10.1149/1.1609997

Direct numerical simulation of electroconvective instability and hydrodynamic chaos near an ion-selective surface
journal, November 2013

  • Druzgalski, C. L.; Andersen, M. B.; Mani, A.
  • Physics of Fluids, Vol. 25, Issue 11
  • DOI: 10.1063/1.4818995

    Works referencing / citing this record:

    In situ formed polymer gel electrolytes for lithium batteries with inherent thermal shutdown safety features
    journal, January 2019

    • Zhou, Hongyao; Liu, Haodong; Li, Yejing
    • Journal of Materials Chemistry A, Vol. 7, Issue 28
    • DOI: 10.1039/c9ta02341k

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.