The electrolyte comprising more robust water and superhalides transforms Zn-metal anode reversibly and dendrite-free

Chong Zhang; Woochul Shin; Liangdong Zhu; Cheng Chen; Joerg C. Neuefeind; Yunkai Xu; Sarah I. Allec; Cong Liu; Zhixuan Wei; Aigerim Daniyar; Jia Xing Jiang; Chong Fang; P. Alex Greaney; Xiulei Ji

doi:10.1002/cey2.70

The electrolyte comprising more robust water and superhalides transforms Zn-metal anode reversibly and dendrite-free

Chong Zhang, Woochul Shin, Liangdong Zhu, Cheng Chen, Joerg C. Neuefeind, Yunkai Xu, Sarah I. Allec, Cong Liu, Zhixuan Wei, Aigerim Daniyar, Jia Xing Jiang, Chong Fang, P. Alex Greaney, Xiulei Ji

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

125 Scopus citations

Abstract

A great challenge for all aqueous batteries, including Zn-metal batteries, is the parasitic hydrogen evolution reaction on the low-potential anode. Herein, we report the formula of a highly concentrated aqueous electrolyte that mitigates hydrogen evolution by transforming water molecules more inert. The electrolyte comprises primarily ZnCl₂ and LiCl as an additive, both of which are inexpensive salts. The O–H covalent bonds in water get strengthened in a chemical environment that has fewer hydrogen bonding interactions and a greater number of Zn–Cl superhalides, as suggested by integrated characterization and simulation. As a result, the average Coulombic efficiency of zinc-metal anode is raised to an unprecedented >99.7% at 1 mA cm⁻². In the new electrolyte, the plating/stripping processes leave the zinc-metal anode dendrite-free, and the zinc-metal anode delivers stable plating/stripping cycles for 4000 hours with an areal capacity of 4 mAh cm⁻² at 2 mA cm⁻². Furthermore, the high Coulombic efficiency of zinc-metal anode in the ZnCl₂-LiCl mixture electrolyte is demonstrated in full cells with a limited anode. The V₂O₅·H₂O||Zn full cell with an N/P mass ratio of 1.2 delivers a stable life of more than 2500 cycles, and the LiMn₂O₄||Zn hybrid cell with an N/P mass ratio of 0.6 exhibits 1500 cycles in its stable life.

Original language	English
Pages (from-to)	339-348
Number of pages	10
Journal	Carbon Energy
Volume	3
Issue number	2
DOIs	https://doi.org/10.1002/cey2.70
State	Published - Jun 2021
Externally published	Yes

Funding

XJ thanks Oregon State University for AID program support. J-XJ thanks the financial support from the National Natural Science Foundation of China (21574077 and 21304055), 111 project (B14041), the Fundamental Research Funds for the Central Universities (GK201801001). CZ is supported by a fellowship from the China Scholarship Council (201706870033) CF is grateful to the U.S. National Science Foundation CAREER grant (CHE-1455353) for the support of the femtosecond stimulated Raman instrumentation and the NSF MRI grant (DMR-1920368) for additional support. The authors declare no conflict of interest. [Correction added on 15 June 2021, after first online publication: Conflict of Interest section has been added.] XJ thanks Oregon State University for AID program support. J‐XJ thanks the financial support from the National Natural Science Foundation of China (21574077 and 21304055), 111 project (B14041), the Fundamental Research Funds for the Central Universities (GK201801001). CZ is supported by a fellowship from the China Scholarship Council (201706870033) CF is grateful to the U.S. National Science Foundation CAREER grant (CHE‐1455353) for the support of the femtosecond stimulated Raman instrumentation and the NSF MRI grant (DMR‐1920368) for additional support.

Funders	Funder number
National Science Foundation	DMR‐1920368, CHE‐1455353
Oregon State University
National Natural Science Foundation of China	21574077, 21304055
China Scholarship Council	201706870033
Fundamental Research Funds for the Central Universities	GK201801001
Higher Education Discipline Innovation Project	B14041

Keywords

LiCl
Zn anode
ZnCl
reversibility
stability
water-in-salt electrolyte

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/cey2.70

Cite this

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title = "The electrolyte comprising more robust water and superhalides transforms Zn-metal anode reversibly and dendrite-free",

abstract = "A great challenge for all aqueous batteries, including Zn-metal batteries, is the parasitic hydrogen evolution reaction on the low-potential anode. Herein, we report the formula of a highly concentrated aqueous electrolyte that mitigates hydrogen evolution by transforming water molecules more inert. The electrolyte comprises primarily ZnCl2 and LiCl as an additive, both of which are inexpensive salts. The O–H covalent bonds in water get strengthened in a chemical environment that has fewer hydrogen bonding interactions and a greater number of Zn–Cl superhalides, as suggested by integrated characterization and simulation. As a result, the average Coulombic efficiency of zinc-metal anode is raised to an unprecedented >99.7% at 1 mA cm−2. In the new electrolyte, the plating/stripping processes leave the zinc-metal anode dendrite-free, and the zinc-metal anode delivers stable plating/stripping cycles for 4000 hours with an areal capacity of 4 mAh cm−2 at 2 mA cm−2. Furthermore, the high Coulombic efficiency of zinc-metal anode in the ZnCl2-LiCl mixture electrolyte is demonstrated in full cells with a limited anode. The V2O5·H2O||Zn full cell with an N/P mass ratio of 1.2 delivers a stable life of more than 2500 cycles, and the LiMn2O4||Zn hybrid cell with an N/P mass ratio of 0.6 exhibits 1500 cycles in its stable life.",

keywords = "LiCl, Zn anode, ZnCl, reversibility, stability, water-in-salt electrolyte",

author = "Chong Zhang and Woochul Shin and Liangdong Zhu and Cheng Chen and Neuefeind, {Joerg C.} and Yunkai Xu and Allec, {Sarah I.} and Cong Liu and Zhixuan Wei and Aigerim Daniyar and Jiang, {Jia Xing} and Chong Fang and {Alex Greaney}, P. and Xiulei Ji",

note = "Publisher Copyright: {\textcopyright} 2020 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.",

year = "2021",

month = jun,

doi = "10.1002/cey2.70",

language = "English",

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T1 - The electrolyte comprising more robust water and superhalides transforms Zn-metal anode reversibly and dendrite-free

AU - Zhang, Chong

AU - Shin, Woochul

AU - Zhu, Liangdong

AU - Chen, Cheng

AU - Neuefeind, Joerg C.

AU - Xu, Yunkai

AU - Allec, Sarah I.

AU - Liu, Cong

AU - Wei, Zhixuan

AU - Daniyar, Aigerim

AU - Jiang, Jia Xing

AU - Fang, Chong

AU - Alex Greaney, P.

AU - Ji, Xiulei

PY - 2021/6

Y1 - 2021/6

N2 - A great challenge for all aqueous batteries, including Zn-metal batteries, is the parasitic hydrogen evolution reaction on the low-potential anode. Herein, we report the formula of a highly concentrated aqueous electrolyte that mitigates hydrogen evolution by transforming water molecules more inert. The electrolyte comprises primarily ZnCl2 and LiCl as an additive, both of which are inexpensive salts. The O–H covalent bonds in water get strengthened in a chemical environment that has fewer hydrogen bonding interactions and a greater number of Zn–Cl superhalides, as suggested by integrated characterization and simulation. As a result, the average Coulombic efficiency of zinc-metal anode is raised to an unprecedented >99.7% at 1 mA cm−2. In the new electrolyte, the plating/stripping processes leave the zinc-metal anode dendrite-free, and the zinc-metal anode delivers stable plating/stripping cycles for 4000 hours with an areal capacity of 4 mAh cm−2 at 2 mA cm−2. Furthermore, the high Coulombic efficiency of zinc-metal anode in the ZnCl2-LiCl mixture electrolyte is demonstrated in full cells with a limited anode. The V2O5·H2O||Zn full cell with an N/P mass ratio of 1.2 delivers a stable life of more than 2500 cycles, and the LiMn2O4||Zn hybrid cell with an N/P mass ratio of 0.6 exhibits 1500 cycles in its stable life.

AB - A great challenge for all aqueous batteries, including Zn-metal batteries, is the parasitic hydrogen evolution reaction on the low-potential anode. Herein, we report the formula of a highly concentrated aqueous electrolyte that mitigates hydrogen evolution by transforming water molecules more inert. The electrolyte comprises primarily ZnCl2 and LiCl as an additive, both of which are inexpensive salts. The O–H covalent bonds in water get strengthened in a chemical environment that has fewer hydrogen bonding interactions and a greater number of Zn–Cl superhalides, as suggested by integrated characterization and simulation. As a result, the average Coulombic efficiency of zinc-metal anode is raised to an unprecedented >99.7% at 1 mA cm−2. In the new electrolyte, the plating/stripping processes leave the zinc-metal anode dendrite-free, and the zinc-metal anode delivers stable plating/stripping cycles for 4000 hours with an areal capacity of 4 mAh cm−2 at 2 mA cm−2. Furthermore, the high Coulombic efficiency of zinc-metal anode in the ZnCl2-LiCl mixture electrolyte is demonstrated in full cells with a limited anode. The V2O5·H2O||Zn full cell with an N/P mass ratio of 1.2 delivers a stable life of more than 2500 cycles, and the LiMn2O4||Zn hybrid cell with an N/P mass ratio of 0.6 exhibits 1500 cycles in its stable life.

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