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:

Ji, Xiao ^[1]; Chen, Ji  ^[2];

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• Search DOE PAGES for ORCID "0000-0003-0326-8304"
• Search orcid.org for ORCID "0000-0003-0326-8304"

Wang, Fei ^[2]; Sun, Wei ^[3]; Ruan, Yunjun  ^[3];

• Search DOE PAGES for author "Ruan, Yunjun"
• Search DOE PAGES for ORCID "0000-0002-0696-8931"
• Search orcid.org for ORCID "0000-0002-0696-8931"

Miao, Ling ^[4]; Jiang, Jianjun ^[4]; Wang, Chunsheng  ^[5]

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• Search DOE PAGES for ORCID "0000-0002-8626-6381"
• Search orcid.org for ORCID "0000-0002-8626-6381"

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+ Show Author Affiliations

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:

2018-09-07

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)