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Title: Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes

Journal Article · · Science Advances

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.

Research Organization:
Cornell Univ., Ithaca, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0016082
OSTI ID:
1499929
Journal Information:
Science Advances, Vol. 4, Issue 3; ISSN 2375-2548
Publisher:
AAASCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 70 works
Citation information provided by
Web of Science

References (45)

Modern Electroplating journal January 1964
Effect of Turbulence on Limiting Current in Electrodialysis Cells journal December 1959
Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries journal October 2015
Review on gel polymer electrolytes for lithium batteries journal January 2006
Electric Birefringence of Electrolytes near Charged Surfaces, II:  Effect of Polymeric Additives journal October 2007
Nonflammable perfluoropolyether-based electrolytes for lithium batteries text January 2014
Modern electroplating journal June 1954
Electrochemical aspects of the generation of ramified metallic electrodeposits journal December 1990
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries. journal May 2006
Role of the membrane surface in concentration polarization at ion-exchange membrane journal January 1988
Highly Stable Sodium Batteries Enabled by Functional Ionic Polymer Membranes journal January 2017
Electric Birefringence of Electrolytes near Charged Surfaces, I journal October 2007
Electrodeposition of composite coatings containing nanoparticles in a metal deposit journal September 2006
Interface layer formation in solid polymer electrolyte lithium batteries: an XPS study journal January 2014
Theory of powdered metal formation in electrochemistry—morphological instability in galvanostatic crystal growth under diffusion control journal November 1981
Transition of lithium growth mechanisms in liquid electrolytes journal January 2016
Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions journal July 2016
Concentration polarization and second-kind electrokinetic instability at an ion-selective surface admitting normal flow journal July 2011
Ion transfer across electrodialysis membranes in the overlimiting current range: stationary voltage current characteristics and current noise power spectra under different conditions of free convection journal July 1992
The cathode–electrolyte interface in the Li-ion battery journal November 2004
Copper Deposition in the Presence of Polyethylene Glycol journal January 1998
Nonflammable perfluoropolyether-based electrolytes for lithium batteries journal February 2014
Effect of Electrolyte Composition on Lithium Dendrite Growth journal January 2008
A stable room-temperature sodium–sulfur battery journal June 2016
Formation of a mesh-like electrodeposit induced by electroconvection journal February 1994
Nanocomposite polymer electrolytes for lithium batteries journal July 1998
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries journal February 2006
Electrical Energy Storage and Intercalation Chemistry journal June 1976
Copper Deposition in the Presence of Polyethylene Glycol: II. Electrochemical Impedance Spectroscopy journal October 1998
Electrodeposition of polymer coatings journal July 1988
Calculation of the space charge in electrodeposition from a binary electrolyte journal February 2006
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
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
Electro-osmotically induced convection at a permselective membrane journal August 2000
Field-Induced Layering of Colloidal Crystals journal May 1996
An EIS Study of the Anode Li/PEO-LiTFSI of a Li Polymer Battery journal January 2003
Branched fractal patterns in non-equilibrium electrochemical deposition from oscillatory nucleation and growth journal November 1997
Direct numerical simulation of electroconvective instability and hydrodynamic chaos near an ion-selective surface journal November 2013
On the coupling between buoyancy forces and electroconvective instability near ion-selective surfaces text January 2016
Drag reduction in turbulent flow by polymer additives journal January 1973
Nonflammable electrolyte enhances battery safety journal February 2014
Equilibrium electro-osmotic instability in concentration polarization at a perfectly charge-selective interface journal September 2017
Coupling between Buoyancy Forces and Electroconvective Instability near Ion-Selective Surfaces journal May 2016

Cited By (11)

Designing solid-state interfaces on lithium-metal anodes: a review journal September 2019
Solid-state polymer electrolytes for high-performance lithium metal batteries journal September 2019
Enabling reversible redox reactions in electrochemical cells using protected LiAl intermetallics as lithium metal anodes journal October 2019
Electroconvection and Morphological Instabilities in Potentiostatic Electrodeposition across Liquid Electrolytes with Polymer Additives journal January 2018
Investigation of the temperature-dependent behaviours of Li metal anode journal January 2019
Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic Li-Na alloy–O2 batteries journal November 2018
Tuning the Electron Density of Aromatic Solvent for Stable Solid-Electrolyte-Interphase Layer in Carbonate-Based Lithium Metal Batteries journal October 2018
Viscoelastic and Nonflammable Interface Design–Enabled Dendrite‐Free and Safe Solid Lithium Metal Batteries journal February 2019
Nip the Sodium Dendrites in the Bud on Planar Doped Graphene in Liquid/Gel Electrolytes journal January 2019
In situ formed polymer gel electrolytes for lithium batteries with inherent thermal shutdown safety features journal January 2019
Electrophoresis in dilute polymer solutions journal December 2019

Figures / Tables (4)


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