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

Wang, Fei; Blanc, Lauren E.; Li, Qin; Faraone, Antonio; Ji, Xiao; Chen‐Mayer, Huaiyu H.; Paul, Rick L.; Dura, Joseph A.; Hu, Enyuan; Xu, Kang; Nazar, Linda F.; Wang, Chunsheng

doi:10.1002/aenm.202102016

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

Journal Article · Mon Oct 04 00:00:00 EDT 2021 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202102016· OSTI ID:1827175

^[1]; Blanc, Lauren E. ^[2]; Li, Qin ^[1]; Faraone, Antonio ^[3]; Ji, Xiao ^[4]; Chen‐Mayer, Huaiyu H. ^[3]; Paul, Rick L. ^[3]; Dura, Joseph A. ^[3]; ^[5]; Xu, Kang ^[6]; Nazar, Linda F. ^[2]; Wang, Chunsheng ^[4]

Fudan Univ., Shanghai (China)
Univ. of Waterloo, ON (Canada)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Univ. of Maryland, College Park, MD (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.
Army Research Lab., Adelphi, MD (United States)

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 Zn_xH_yVPO₄F 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|Zn_xH_yVPO₄F.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AR0000389; SC0012704

OSTI ID:: 1827175

Report Number(s):: BNL-222252-2021--JAAM

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 41 Vol. 11; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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

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