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Title: Water-Activated VOPO 4 for Magnesium Ion Batteries

Abstract

Rechargeable Mg batteries, using high capacity and dendrite-free Mg metal anodes, are promising energy storage devices for large scale smart grid due to low cost and high safety. However, the performance of Mg batteries is still plagued by the slow reaction kinetics of their cathode materials. Recent discoveries demonstrate that water in cathode can significantly enhance the Mg-ion diffusion in cathode by an unknown mechanism. Here, we propose the water-activated layered-structure VOPO4 as a novel cathode material and examine the impact of water in electrode or organic electrolyte on the thermodynamics and kinetics of Mg-ion intercalation/deintercalation in cathodes. Electrochemical measurements verify that water in both VOPO4 lattice and organic electrolyte can largely activate VOPO4 cathode. Thermodynamic analysis demonstrates that the water in the electrolyte will equilibrate with the structural water in VOPO4 lattice, and the water activity in the electrolyte alerts the mechanism and kinetics for electrochemical Mg-ion intercalation in VOPO4. Theoretical calculations and experimental results demonstrate that water reduces both the solid-state diffusion barrier in the VOPO4 electrode and the desolvation penalty at the interface. To achieve fast reaction kinetics, the water activity in the electrolyte should be larger than 10–2. The proposed activation mechanism provides guidance for screeningmore » and designing novel chemistry for high performance multivalent-ion batteries.« less

Authors:
 [1]; ORCiD logo [2];  [2];  [3]; ORCiD logo [3];  [4];  [4]; ORCiD logo [5]
  1. Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Huazhong Univ. of Science and Technology, Wuhan (China). School of Optical and Electronic Information
  2. Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering
  3. Huazhong Univ. of Science and Technology, Wuhan (China). School of Optical and Electronic Information
  4. School of Optical and Electronic Information, Huazhong University of Science and Technology, 430074 Wuhan, Hubei, China
  5. Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering, and Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES); Univ. of Maryland, College Park, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1566550
Grant/Contract Number:  
SC0001160
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 18; Journal Issue: 10; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; bio-inspired, energy storage (including batteries and capacitors), defects, charge transport, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Ji, Xiao, Chen, Ji, Wang, Fei, Sun, Wei, Ruan, Yunjun, Miao, Ling, Jiang, Jianjun, and Wang, Chunsheng. Water-Activated VOPO 4 for Magnesium Ion Batteries. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.nanolett.8b02854.
Ji, Xiao, Chen, Ji, Wang, Fei, Sun, Wei, Ruan, Yunjun, Miao, Ling, Jiang, Jianjun, & Wang, Chunsheng. Water-Activated VOPO 4 for Magnesium Ion Batteries. United States. https://doi.org/10.1021/acs.nanolett.8b02854
Ji, Xiao, Chen, Ji, Wang, Fei, Sun, Wei, Ruan, Yunjun, Miao, Ling, Jiang, Jianjun, and Wang, Chunsheng. Fri . "Water-Activated VOPO 4 for Magnesium Ion Batteries". United States. https://doi.org/10.1021/acs.nanolett.8b02854. https://www.osti.gov/servlets/purl/1566550.
@article{osti_1566550,
title = {Water-Activated VOPO 4 for Magnesium Ion Batteries},
author = {Ji, Xiao and Chen, Ji and Wang, Fei and Sun, Wei and Ruan, Yunjun and Miao, Ling and Jiang, Jianjun and Wang, Chunsheng},
abstractNote = {Rechargeable Mg batteries, using high capacity and dendrite-free Mg metal anodes, are promising energy storage devices for large scale smart grid due to low cost and high safety. However, the performance of Mg batteries is still plagued by the slow reaction kinetics of their cathode materials. Recent discoveries demonstrate that water in cathode can significantly enhance the Mg-ion diffusion in cathode by an unknown mechanism. Here, we propose the water-activated layered-structure VOPO4 as a novel cathode material and examine the impact of water in electrode or organic electrolyte on the thermodynamics and kinetics of Mg-ion intercalation/deintercalation in cathodes. Electrochemical measurements verify that water in both VOPO4 lattice and organic electrolyte can largely activate VOPO4 cathode. Thermodynamic analysis demonstrates that the water in the electrolyte will equilibrate with the structural water in VOPO4 lattice, and the water activity in the electrolyte alerts the mechanism and kinetics for electrochemical Mg-ion intercalation in VOPO4. Theoretical calculations and experimental results demonstrate that water reduces both the solid-state diffusion barrier in the VOPO4 electrode and the desolvation penalty at the interface. To achieve fast reaction kinetics, the water activity in the electrolyte should be larger than 10–2. The proposed activation mechanism provides guidance for screening and designing novel chemistry for high performance multivalent-ion batteries.},
doi = {10.1021/acs.nanolett.8b02854},
journal = {Nano Letters},
number = 10,
volume = 18,
place = {United States},
year = {2018},
month = {9}
}

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