Rate Dependent Multi-Mechanism Discharge of Ag0.50VOP 4·1.8H2O: Insights from In Situ Energy Dispersive X-ray Diffraction

Huie, Matthew M.; Bock, David C.; Zhong, Zhong; Bruck, Andrea M.; Yin, Jiefu; Takeuchi, Esther S.; Takeuchi, Kenneth J.; Marschilok, Amy C.

doi:10.1149/2.0011701jes

Title: Rate Dependent Multi-Mechanism Discharge of Ag_0.50VOP ₄·1.8H₂O: Insights from In Situ Energy Dispersive X-ray Diffraction

Journal Article · Thu Sep 01 00:00:00 EDT 2016 · Journal of the Electrochemical Society

DOI: https://doi.org/10.1149/2.0011701jes · OSTI ID:1376103

Huie, Matthew M. ^[1]; Bock, David C. ^[2]; Zhong, Zhong ^[2]; Bruck, Andrea M. ^[3]; Yin, Jiefu ^[3]; Takeuchi, Esther S. ^[4]; Takeuchi, Kenneth J. ^[5]; Marschilok, Amy C. ^[5]

Stony Brook Univ., NY (United States). Department of Materials Science and Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
Stony Brook Univ., NY (United States). Dept. of Chemistry
Stony Brook Univ., NY (United States). Department of Materials Science and Engineering and Department of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
Stony Brook Univ., NY (United States). Department of Materials Science and Engineering and Department of Chemistry

Ag_0.50VOPO₄·1.8H₂O (silver vanadium phosphate, SVOP) demonstrates a counterintuitive higher initial loaded voltage under higher discharge current. Energy dispersive X-ray diffraction (EDXRD) from synchrotron radiation was used to create tomographic profiles of cathodes at various depths of discharge for two discharge rates. SVOP displays two reduction mechanisms, reduction of a vanadium center accompanied by lithiation of the structure, or reduction-displacement of a silver cation to form silver metal. In-situ EDXRD provides the opportunity to observe spatially resolved changes to the parent SVOP crystal and formation of Ag⁰ during reduction. At a C/170 discharge rate V⁵⁺ reduction is the preferred initial reaction resulting in higher initial loaded voltage. At a discharge rate of C/400 reduction of Ag⁺ with formation of conductive Ag⁰ occurs earlier during discharge. Discharge rate also affects the spatial location of reduction products. The faster discharge rate initiates reduction close to the current collector with non-uniform distribution of silver metal resulting in isolated cathode areas. The slower rate develops a more homogenous distribution of reduced SVOP and silver metal. This study illuminates the roles of electronic and ionic conductivity limitations within a cathode at the mesoscale and how they impact the course of reduction processes and loaded voltage.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704; SC0012673

OSTI ID:: 1376103

Report Number(s):: BNL--113937-2017-JA

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 1 Vol. 164; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cathode material
energy dispersive x-ray diffraction
lithium battery
silver vanadium phosphorous oxide

Title: Rate Dependent Multi-Mechanism Discharge of Ag0.50VOP 4·1.8H2O: Insights from In Situ Energy Dispersive X-ray Diffraction

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Title: Rate Dependent Multi-Mechanism Discharge of Ag_0.50VOP ₄·1.8H₂O: Insights from In Situ Energy Dispersive X-ray Diffraction