skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Quantifying and Suppressing Proton Intercalation to Enable High-Voltage Zn-Ion Batteries

Journal Article · · Advanced Energy Materials
ORCiD logo [1];  [2];  [1];  [3];  [4];  [3];  [3];  [3]; ORCiD logo [5];  [6];  [2];  [4]
  1. Fudan Univ., Shanghai (China)
  2. Univ. of Waterloo, ON (Canada)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  4. Univ. of Maryland, College Park, MD (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.
  6. Army Research Lab., Adelphi, MD (United States)
+ Show Author Affiliations

Rechargeable Zn-ion batteries (ZIBs) are widely regarded as promising candidates for large-scale energy storage applications. Like most multivalent battery systems (based on Zn, Mg, Ca, etc.), further progress in ZIB development relies on the discovery and design of novel cathode hosts capable of reversible Zn2+ (de)intercalation. This work employs VPO4F as a ZIB cathode and explores ensuing intercalation mechanisms along with interfacial dynamics during cycling to quantify the water dynamics in concentrated electrolytes and/or hybrid aqueous-non aqueous (HANEs) electrolyte(s). Like most oxide-based cathode materials, proton (H+) intercalation dominates electrochemical activity during discharge of ZnxHyVPO4F in aqueous media due to the hydroxylated nature of the interface. Such H+ electrochemistry diminishes low-rate and/or long-term electrochemical performance of ZIBs which inhibits implementation for practical applications. Thus, quantification of the water dynamics in various electrolytes is demonstrated for the first time. Detailed investigations of water mobility in various concentrated electrolytes and HANEs systems enable the design of an electrolyte that enhances aqueous anodic stability and suppresses water/proton activity during discharge. Tuning Zn2+/H+ intercalation kinetics simultaneously allows for a high voltage (1.9 V) and long-lasting aqueous zinc-ion battery: Zn|Zn(OTf)2·nH2O-PC|ZnxHyVPO4F.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office; USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; AR0000389
OSTI ID:
1827175
Report Number(s):
BNL-222252-2021-JAAM
Journal Information:
Advanced Energy Materials, Vol. 11, Issue 41; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (55)

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
Electrochemically induced spinel-layered phase transition of Mn3O4 in high performance neutral aqueous rechargeable zinc battery journal January 2018
Cation-Deficient Spinel ZnMn 2 O 4 Cathode in Zn(CF 3 SO 3 ) 2 Electrolyte for Rechargeable Aqueous Zn-Ion Battery journal September 2016
Aqueous Zn//Zn(CF3SO3)2//Na3V2(PO4)3 batteries with simultaneous Zn2+/Na+ intercalation/de-intercalation journal April 2019
Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges journal February 2017
Electrochemical Property:  Structure Relationships in Monoclinic Li 3 - y V 2 (PO 4 ) 3 journal August 2003
Energetic Zinc Ion Chemistry: The Rechargeable Zinc Ion Battery journal December 2011
Zn/MnO 2 Battery Chemistry With H + and Zn 2+ Coinsertion journal July 2017
Full open-framework batteries for stationary energy storage journal January 2014
Aqueous rechargeable zinc/sodium vanadate batteries with enhanced performance from simultaneous insertion of dual carriers journal April 2018
Accessing the 2 V VV/VIV redox process of vanadyl phosphate cathode for aqueous batteries journal September 2021
Na 3 MnZr(PO 4 ) 3 : A High-Voltage Cathode for Sodium Batteries journal December 2018
NASICON Na 3 V 2 (PO 4 ) 3 Enables Quasi-Two-Stage Na + and Zn 2+ Intercalation for Multivalent Zinc Batteries journal March 2020
A Highly Reversible Zn Anode with Intrinsically Safe Organic Electrolyte for Long‐Cycle‐Life Batteries journal June 2019
Charge storage mechanism of MnO 2 cathodes in Zn/MnO 2 batteries using ionic liquid-based gel polymer electrolytes journal November 2015
Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities journal September 2017
Hybrid Aqueous/Non-aqueous Electrolyte for Safe and High-Energy Li-Ion Batteries journal May 2018
A New Strategy for High-Voltage Cathodes for K-Ion Batteries: Stoichiometric KVPO 4 F journal July 2018
Towards High-Voltage Aqueous Metal-Ion Batteries Beyond 1.5 V: The Zinc/Zinc Hexacyanoferrate System journal September 2014
An organic/inorganic electrode-based hydronium-ion battery journal February 2020
Reversible aqueous zinc/manganese oxide energy storage from conversion reactions journal April 2016
Effects of Inorganic Cation Templates on Octahedral Molecular Sieves of Manganese Oxide journal November 1994
Hydrated Intercalation for High‐Performance Aqueous Zinc Ion Batteries journal February 2019
Towards a calcium-based rechargeable battery journal October 2015
Achieving Both High Voltage and High Capacity in Aqueous Zinc‐Ion Battery for Record High Energy Density journal September 2019
Issues and opportunities facing aqueous zinc-ion batteries journal January 2019
A High‐Energy NASICON‐Type Cathode Material for Na‐Ion Batteries journal March 2020
Role of Structural H 2 O in Intercalation Electrodes: The Case of Mg in Nanocrystalline Xerogel-V 2 O 5 journal March 2016
H + ‐Insertion Boosted α‐MnO 2 for an Aqueous Zn‐Ion Battery journal January 2020
Present and Future Perspective on Electrode Materials for Rechargeable Zinc-Ion Batteries journal September 2018
Origin of Electrochemical, Structural, and Transport Properties in Nonaqueous Zinc Electrolytes journal January 2016
Reversible Multivalent (Monovalent, Divalent, Trivalent) Ion Insertion in Open Framework Materials journal April 2015
How Water Accelerates Bivalent Ion Diffusion at the Electrolyte/Electrode Interface journal August 2018
Oxide versus Nonoxide Cathode Materials for Aqueous Zn Batteries: An Insight into the Charge Storage Mechanism and Consequences Thereof journal December 2018
Design strategies for nonaqueous multivalent-ion and monovalent-ion battery anodes journal February 2020
A High Power Rechargeable Nonaqueous Multivalent Zn/V 2 O 5 Battery journal August 2016
Investigation of Alkali‐Ion (Li, Na, and K) Intercalation in K x VPO 4 F ( x ∼ 0) Cathode journal June 2019
Aqueous vs. nonaqueous Zn-ion batteries: consequences of the desolvation penalty at the interface journal January 2018
Prussian Blue Analogs as Battery Materials journal October 2018
The path towards sustainable energy journal December 2016
Investigation of the Mechanism of Mg Insertion in Birnessite in Nonaqueous and Aqueous Rechargeable Mg-Ion Batteries journal January 2016
Synthesis and Crystallographic Study of Homeotypic LiVPO 4 F and LiVPO 4 O journal February 2012
Layered Mg x V 2 O 5 · n H 2 O as Cathode Material for High-Performance Aqueous Zinc Ion Batteries journal September 2018
Delithiation/lithiation behaviors of three polymorphs of LiVOPO 4 journal January 2018
Highly Stable Aqueous Zinc-Ion Storage Using a Layered Calcium Vanadium Oxide Bronze Cathode journal February 2018
Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries journal May 2019
Achieving High‐Voltage and High‐Capacity Aqueous Rechargeable Zinc Ion Battery by Incorporating Two‐Species Redox Reaction journal October 2019
Inhibiting VOPO 4 ⋅ x  H 2 O Decomposition and Dissolution in Rechargeable Aqueous Zinc Batteries to Promote Voltage and Capacity Stabilities journal November 2019
A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode journal August 2016
LiVPO 4 F 1– y O y Tavorite-Type Compositions: Influence of the Concentration of Vanadyl-Type Defects on the Structure and Electrochemical Performance journal July 2018
Structure and Electrochemistry of Two-Electron Redox Couples in Lithium Metal Fluorophosphates Based on the Tavorite Structure journal December 2011
A profile refinement method for nuclear and magnetic structures journal June 1969
Highly reversible zinc metal anode for aqueous batteries journal April 2018
Layered vanadium oxides with proton and zinc ion insertion for zinc ion batteries journal October 2019
Scientific Challenges for the Implementation of Zn-Ion Batteries journal April 2020

Similar Records

Tuning Discharge Behavior of Hollandite α-MnO2 in Hydrated Zinc Ion Battery by Transition Metal Substitution
Journal Article · Fri Jan 06 00:00:00 EST 2023 · Journal of Physical Chemistry. C · OSTI ID:1827175
+2 more
Discharging Behavior of Hollandite α-MnO2 in a Hydrated Zinc-Ion Battery
Journal Article · Mon Dec 13 00:00:00 EST 2021 · ACS Applied Materials and Interfaces · OSTI ID:1827175
+5 more
Tuning the Solvation Structure in Aqueous Zinc Batteries to Maximize Zn-Ion Intercalation and Optimize Dendrite-Free Zinc Plating
Journal Article · Mon Jan 03 00:00:00 EST 2022 · ACS Energy Letters · OSTI ID:1827175
+3 more

Related Subjects

25 ENERGY STORAGE
Zn-ion batteries
proton intercalation
x-ray absorption spectroscopy