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Title: Battery Relevant Electrochemistry of Ag7Fe3(P2O7 )4 : Contrasting Contributions from the Redox Chemistries of Ag+ and Fe3+

Journal Article · · Chemistry of Materials
 [1];  [2];  [3];  [4];  [3]
  1. Stony Brook Univ., NY (United States). Dept. of Chemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Stony Brook Univ., NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering
  4. Stony Brook Univ., NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering
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Ag7Fe3(P2O7 )4 is an example of an electrochemical displacement material which contains two different electrochemically active metal cations, where one cation (Ag+) forms metallic silver nanoparticles external to the crystals of Ag7Fe3(P2O7 )4 via an electrochemical reduction displacement reaction, while the other cation (Fe+3) is electrochemically reduced with the retention of iron cations within the anion structural framework concomitant with lithium insertion. These contrasting redox chemistries within one pure cathode material enable high rate capability and reversibility when Ag7Fe3(P2O7 )4 is employed as cathode material in a lithium ion battery (LIB). Further, pyrophosphate materials are thermally and electrically stable, desirable attributes for cathode materials in LIBs. In this article, a bimetallic pyrophosphate material Ag7Fe3(P2O7 )4 is synthesized and confirmed to be a single phase by Rietveld refinement. Electrochemistry of Ag7Fe3(P2O7 )4 is reported for the first time in the context of lithium based batteries using cyclic voltammetry and galvanostatic discharge–charge cycling. The reduction displacement reaction and the lithium (de)insertion processes are investigated using ex situ X-ray absorption spectroscopy and X-ray diffraction of electrochemically reduced and oxidized Ag7Fe3(P2O7 )4. Ag7Fe3(P2O7 )4 exhibits good reversibility at the iron centers indicated by ~80% capacity retention over 100 cycles following the initial formation cycle and excellent rate capability exhibited by ~70% capacity retention upon a 4-fold increase in current.

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); Gertrude and Maurice Goldhaber Distinguished Fellowship
Grant/Contract Number:
SC0012704; SC0008512; SC001267; AC02-98CH10886
OSTI ID:
1341695
Report Number(s):
BNL-113440-2017-JA; TRN: US1701528
Journal Information:
Chemistry of Materials, Vol. 28, Issue 21; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright 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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Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques journal January 2017
Mg 2+ storage and mobility in anatase TiO 2 : the role of frustrated coordination journal January 2019

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Related Subjects

25 ENERGY STORAGE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
electrochemistry
redox
Ag+
Fe3+
cathode
material