Origin of Electrochemical, Structural, and Transport Properties in Nonaqueous Zinc Electrolytes

Sang Don Han; Nav Nidhi Rajput; Xiaohui Qu; Baofei Pan; Meinan He; Magali S. Ferrandon; Chen Liao; Kristin A. Persson; Anthony K. Burrell

doi:10.1021/acsami.5b10024

Origin of Electrochemical, Structural, and Transport Properties in Nonaqueous Zinc Electrolytes

Sang Don Han
, Nav Nidhi Rajput
, Xiaohui Qu
, Baofei Pan
, Meinan He
, Magali S. Ferrandon
, Chen Liao
, Kristin A. Persson
, Anthony K. Burrell

Materials Science and Engineering

Argonne National Laboratory
Lawrence Berkeley National Laboratory
Worcester Polytechnic Institute

Research output: Contribution to journal › Article › peer-review

222 Scopus citations

Abstract

Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile-Zn(TFSI)₂, acetonitrile-Zn(CF₃SO₃)₂, and propylene carbonate-Zn(TFSI)₂ electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99% of Coulombic efficiency) but also provide high anodic stability (up to ∼3.8 V vs Zn/Zn²⁺). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates that the solvents play an important role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. The combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes.

Original language	English
Pages (from-to)	3021-3031
Number of pages	11
Journal	ACS Applied Materials and Interfaces
Volume	8
Issue number	5
DOIs	https://doi.org/10.1021/acsami.5b10024
State	Published - Feb 17 2016

Keywords

anodic stability
Coulombic efficiency
electrode/electrolyte interface
nonaqueous electrolyte
reversible deposition
solvation structure

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10.1021/acsami.5b10024

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title = "Origin of Electrochemical, Structural, and Transport Properties in Nonaqueous Zinc Electrolytes",

abstract = "Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile-Zn(TFSI)2, acetonitrile-Zn(CF3SO3)2, and propylene carbonate-Zn(TFSI)2 electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99\% of Coulombic efficiency) but also provide high anodic stability (up to ∼3.8 V vs Zn/Zn2+). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates that the solvents play an important role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. The combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes.",

keywords = "anodic stability, Coulombic efficiency, electrode/electrolyte interface, nonaqueous electrolyte, reversible deposition, solvation structure",

author = "Han, \{Sang Don\} and Rajput, \{Nav Nidhi\} and Xiaohui Qu and Baofei Pan and Meinan He and Ferrandon, \{Magali S.\} and Chen Liao and Persson, \{Kristin A.\} and Burrell, \{Anthony K.\}",

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T1 - Origin of Electrochemical, Structural, and Transport Properties in Nonaqueous Zinc Electrolytes

AU - Han, Sang Don

AU - Rajput, Nav Nidhi

AU - Qu, Xiaohui

AU - Pan, Baofei

AU - He, Meinan

AU - Ferrandon, Magali S.

AU - Liao, Chen

AU - Persson, Kristin A.

AU - Burrell, Anthony K.

PY - 2016/2/17

Y1 - 2016/2/17

N2 - Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile-Zn(TFSI)2, acetonitrile-Zn(CF3SO3)2, and propylene carbonate-Zn(TFSI)2 electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99% of Coulombic efficiency) but also provide high anodic stability (up to ∼3.8 V vs Zn/Zn2+). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates that the solvents play an important role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. The combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes.

AB - Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile-Zn(TFSI)2, acetonitrile-Zn(CF3SO3)2, and propylene carbonate-Zn(TFSI)2 electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99% of Coulombic efficiency) but also provide high anodic stability (up to ∼3.8 V vs Zn/Zn2+). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates that the solvents play an important role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. The combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes.

KW - anodic stability

KW - Coulombic efficiency

KW - electrode/electrolyte interface

KW - nonaqueous electrolyte

KW - reversible deposition

KW - solvation structure

UR - https://www.scopus.com/pages/publications/84958012570

U2 - 10.1021/acsami.5b10024

DO - 10.1021/acsami.5b10024

M3 - Article

AN - SCOPUS:84958012570

SN - 1944-8244

VL - 8

SP - 3021

EP - 3031

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 5

ER -

Origin of Electrochemical, Structural, and Transport Properties in Nonaqueous Zinc Electrolytes

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Keywords

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