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Title: Water-Activated VOPO 4 for Magnesium Ion Batteries

Journal Article · · Nano Letters
 [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

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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES); Univ. of Maryland, College Park, MD (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001160
OSTI ID:
1566550
Journal Information:
Nano Letters, Vol. 18, Issue 10; ISSN 1530-6984
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (35)

Electrochemical Energy Storage for Green Grid journal May 2011
Ultimate Limits to Intercalation Reactions for Lithium Batteries journal October 2014
Sustainability and in situ monitoring in battery development journal December 2016
Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries journal January 2012
Aprotic and Aqueous Li–O2 Batteries journal April 2014
Rechargeable Lithium–Sulfur Batteries journal July 2014
Research Development on Sodium-Ion Batteries journal October 2014
Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges journal February 2017
Status and challenge of Mg battery cathode journal January 2016
Prototype systems for rechargeable magnesium batteries journal October 2000
Magnesium Insertion in Vanadium Oxides: A Structural Study journal January 1994
Electrochemical insertion of magnesium ions into V2O5 from aprotic electrolytes with varied water content journal October 2004
Unraveling the Magnesium-Ion Intercalation Mechanism in Vanadium Pentoxide in a Wet Organic Electrolyte by Structural Determination journal June 2017
The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries journal May 2015
Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host journal April 2015
Preparation of Cathode Active Material for Rechargeable Magnesium Battery by Atmospheric Pressure Microwave Discharge Using Carbon Felt Pieces journal March 2008
Layered TiS 2 Positive Electrode for Mg Batteries journal June 2016
Vanadium phosphate as a promising high-voltage magnesium ion (de)-intercalation cathode host journal January 2015
Mg Intercalation in Layered and Spinel Host Crystal Structures for Mg Batteries journal April 2015
Evaluation of sulfur spinel compounds for multivalent battery cathode applications journal January 2016
Highly Reversible Open Framework Nanoscale Electrodes for Divalent Ion Batteries journal October 2013
Aqueous Mg-Ion Battery Based on Polyimide Anode and Prussian Blue Cathode journal April 2017
Electrochemical Intercalation of Mg 2+ into Anhydrous and Hydrated Crystalline Tungsten Oxides journal July 2017
A Brief Review on Multivalent Intercalation Batteries with Aqueous Electrolytes journal February 2016
Magnesium-ion battery-relevant electrochemistry of MgMn 2 O 4 : crystallite size effects and the notable role of electrolyte water content journal January 2017
Magnesium insertion electrodes for rechargeable nonaqueous batteries — a competitive alternative to lithium? journal September 1999
On the Way to Rechargeable Mg Batteries: The Challenge of New Cathode Materials journal February 2010
Electrochemical Insertion of Magnesium in Metal Oxides and Sulfides from Aprotic Electrolytes journal January 1993
Direct Observation of an Anomalous Spinel-to-Layered Phase Transition Mediated by Crystal Water Intercalation journal October 2015
Electrochemical Insertion of Magnesium into Hydrated Vanadium Bronzes journal January 1995
Water and Thermal Management in Solid‐Polymer‐Electrolyte Fuel Cells journal May 1993
Role of Structural H 2 O in Intercalation Electrodes: The Case of Mg in Nanocrystalline Xerogel-V 2 O 5 journal March 2016
Structural Evolution of Reversible Mg Insertion into a Bilayer Structure of V 2 O 5 · n H 2 O Xerogel Material journal April 2016
How Water Accelerates Bivalent Ion Diffusion at the Electrolyte/Electrode Interface journal August 2018
A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode journal August 2016

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Electrochemical Exchange Reaction Mechanism and the Role of Additive Water to Stabilize the Structure of VOPO 4 ⋅2 H 2 O as a Cathode Material for Potassium‐Ion Batteries journal February 2019
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Ultrahigh Nitrogen Doping of Carbon Nanosheets for High Capacity and Long Cycling Potassium Ion Storage journal October 2019
The Rechargeable Aluminum Battery: Opportunities and Challenges journal August 2019
Water in Rechargeable Multivalent-Ion Batteries: An Electrochemical Pandora's Box journal January 2019
Recent Progress on Layered Cathode Materials for Nonaqueous Rechargeable Magnesium Batteries journal October 2019
Organic quinones towards advanced electrochemical energy storage: recent advances and challenges journal January 2019
Vanadium‐Based Nanomaterials: A Promising Family for Emerging Metal‐Ion Batteries journal January 2020
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