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

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.0011701jes· OSTI ID:1376103
 [1];  [2];  [2];  [3];  [3];  [4];  [5];  [5]
  1. Stony Brook Univ., NY (United States). Department of Materials Science and Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  3. Stony Brook Univ., NY (United States). Dept. of Chemistry
  4. 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;
  5. Stony Brook Univ., NY (United States). Department of Materials Science and Engineering and Department of Chemistry
+ Show Author Affiliations

Ag0.50VOPO4·1.8H2O (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.

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)
Grant/Contract Number:
SC0012704; SC0012673
OSTI ID:
1376103
Report Number(s):
BNL-113937-2017-JA
Journal Information:
Journal of the Electrochemical Society, Vol. 164, Issue 1; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

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Related Subjects

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