Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag7Fe3(P2O7)4)
Abstract
The formation of conductive metallic silver upon electrochemical reduction and lithiation of Ag7Fe3(P2O7)4 is investigated. Alternating current impedance spectroscopy measurements show a 34% decrease in charge transfer resistance upon one electron equivalent (ee) of reduction, which is coincident with the formation of a Ag metal conductive network evidenced by both ex situ and operando X-ray diffraction. Quantitative assessment of Ag metal formation derived from operando XRD shows that only Ag+ ions are reduced during the first 3ee, followed by simultaneous reduction of Ag+ and Fe3+ reduction for the next 5ee (3ee to 8ee), culminating in reduction of the remaining Ag+. Scanning electron microscopy images show smaller Ag metal crystallite size and shorter nearest neighbor distance between and among Ag particles with higher depth of discharge. A high rate intermittent pulsatile discharge test is conducted where the cell delivers 12 total pulses during full discharge to probe the effect of Ag metal formation on the Li/Ag7Fe3(P2O7)4 cell electrochemistry. The Ohmic resistance is derived from the voltage drop of each pulse. The resistance is 65 Ω initially, reaches its minimum of 26 Ω at 4.5 ee discharge, and levels off at 35 Ω after 7.0 ee reduction. In conclusion, the initial Agmore »
- Authors:
-
[3];
[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 Chemistry; Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
- 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 Chemical Engineering
- Stony Brook Univ., NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1376168
- Report Number(s):
- BNL-114140-2017-JA
Journal ID: ISSN 1932-7447
- Grant/Contract Number:
- SC0012704; SC0012673; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 22; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Zhang, Yiman, Kirshenbaum, Kevin C., Marschilok, Amy C., Takeuchi, Esther S., and Takeuchi, Kenneth J. Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag7Fe3(P2O7)4). United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b03723.
Zhang, Yiman, Kirshenbaum, Kevin C., Marschilok, Amy C., Takeuchi, Esther S., & Takeuchi, Kenneth J. Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag7Fe3(P2O7)4). United States. https://doi.org/10.1021/acs.jpcc.7b03723
Zhang, Yiman, Kirshenbaum, Kevin C., Marschilok, Amy C., Takeuchi, Esther S., and Takeuchi, Kenneth J. Thu .
"Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag7Fe3(P2O7)4)". United States. https://doi.org/10.1021/acs.jpcc.7b03723. https://www.osti.gov/servlets/purl/1376168.
@article{osti_1376168,
title = {Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag7Fe3(P2O7)4)},
author = {Zhang, Yiman and Kirshenbaum, Kevin C. and Marschilok, Amy C. and Takeuchi, Esther S. and Takeuchi, Kenneth J.},
abstractNote = {The formation of conductive metallic silver upon electrochemical reduction and lithiation of Ag7Fe3(P2O7)4 is investigated. Alternating current impedance spectroscopy measurements show a 34% decrease in charge transfer resistance upon one electron equivalent (ee) of reduction, which is coincident with the formation of a Ag metal conductive network evidenced by both ex situ and operando X-ray diffraction. Quantitative assessment of Ag metal formation derived from operando XRD shows that only Ag+ ions are reduced during the first 3ee, followed by simultaneous reduction of Ag+ and Fe3+ reduction for the next 5ee (3ee to 8ee), culminating in reduction of the remaining Ag+. Scanning electron microscopy images show smaller Ag metal crystallite size and shorter nearest neighbor distance between and among Ag particles with higher depth of discharge. A high rate intermittent pulsatile discharge test is conducted where the cell delivers 12 total pulses during full discharge to probe the effect of Ag metal formation on the Li/Ag7Fe3(P2O7)4 cell electrochemistry. The Ohmic resistance is derived from the voltage drop of each pulse. The resistance is 65 Ω initially, reaches its minimum of 26 Ω at 4.5 ee discharge, and levels off at 35 Ω after 7.0 ee reduction. In conclusion, the initial Ag reduction is more significant for the conductive network formation indicated by the decrease of both Rct and Ohmic resistance, which facilitates the high power output of the cell.},
doi = {10.1021/acs.jpcc.7b03723},
journal = {Journal of Physical Chemistry. C},
number = 22,
volume = 121,
place = {United States},
year = {2017},
month = {5}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 2 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Pyrophosphate Chemistry toward Safe Rechargeable Batteries
journal, June 2013
- Tamaru, Mao; Chung, Sai Cheong; Shimizu, Daisuke
- Chemistry of Materials, Vol. 25, Issue 12
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997
- Padhi, A. K.
- Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
Na 2 FeP 2 O 7 as a Promising Iron-Based Pyrophosphate Cathode for Sodium Rechargeable Batteries: A Combined Experimental and Theoretical Study
journal, October 2012
- Kim, Heejin; Shakoor, R. A.; Park, Chansun
- Advanced Functional Materials, Vol. 23, Issue 9
Iron and Manganese Pyrophosphates as Cathodes for Lithium-Ion Batteries
journal, January 2011
- Zhou, Hui; Upreti, Shailesh; Chernova, Natasha A.
- Chemistry of Materials, Vol. 23, Issue 2
New Lithium Iron Pyrophosphate as 3.5 V Class Cathode Material for Lithium Ion Battery
journal, October 2010
- Nishimura, Shin-ichi; Nakamura, Megumi; Natsui, Ryuichi
- Journal of the American Chemical Society, Vol. 132, Issue 39
Neutron and X-ray Diffraction Study of Pyrophosphate-Based Li 2– x MP 2 O 7 (M = Fe, Co) for Lithium Rechargeable Battery Electrodes
journal, September 2011
- Kim, Hyungsub; Lee, Seongsu; Park, Young-Uk
- Chemistry of Materials, Vol. 23, Issue 17
Site-Specific Transition Metal Occupation in Multicomponent Pyrophosphate for Improved Electrochemical and Thermal Properties in Lithium Battery Cathodes: A Combined Experimental and Theoretical Study
journal, July 2012
- Shakoor, Rana. A.; Kim, Heejin; Cho, Woosuk
- Journal of the American Chemical Society, Vol. 134, Issue 28
Lithium insertion into Fe2(SO4)3 frameworks
journal, May 1989
- Manthiram, A.; Goodenough, J. B.
- Journal of Power Sources, Vol. 26, Issue 3-4
Electrochemical performance of Li2FeSiO4 as a new Li-battery cathode material
journal, February 2005
- Nytén, Anton; Abouimrane, Ali; Armand, Michel
- Electrochemistry Communications, Vol. 7, Issue 2
Electrochemical Insertion Properties of the Novel Lithium Vanadium Fluorophosphate, LiVPO[sub 4]F
journal, January 2003
- Barker, J.; Saidi, M. Y.; Swoyer, J. L.
- Journal of The Electrochemical Society, Vol. 150, Issue 10
Electronically conductive phospho-olivines as lithium storage electrodes
journal, September 2002
- Chung, Sung-Yoon; Bloking, Jason T.; Chiang, Yet-Ming
- Nature Materials, Vol. 1, Issue 2, p. 123-128
Approaching Theoretical Capacity of LiFePO[sub 4] at Room Temperature at High Rates
journal, January 2001
- Huang, H.; Yin, S. -C.; Nazar, L. F.
- Electrochemical and Solid-State Letters, Vol. 4, Issue 10
Synthesis of LiFePO[sub 4] Nanoparticles in Polyol Medium and Their Electrochemical Properties
journal, January 2006
- Kim, Dong-Han; Kim, Jaekook
- Electrochemical and Solid-State Letters, Vol. 9, Issue 9
Effect of Structure on the Fe[sup 3+]∕Fe[sup 2+] Redox Couple in Iron Phosphates
journal, January 1997
- Padhi, A. K.
- Journal of The Electrochemical Society, Vol. 144, Issue 5
Na 2 FeP 2 O 7 : A Safe Cathode for Rechargeable Sodium-ion Batteries
journal, August 2013
- Barpanda, Prabeer; Liu, Guandong; Ling, Chris D.
- Chemistry of Materials, Vol. 25, Issue 17
Sodium-ion battery cathodes Na 2 FeP 2 O 7 and Na 2 MnP 2 O 7 : diffusion behaviour for high rate performance
journal, January 2014
- Clark, John M.; Barpanda, Prabeer; Yamada, Atsuo
- J. Mater. Chem. A, Vol. 2, Issue 30
Redesign of Li 2 MP 2 O 7 (M = Fe or Mn) by Tuning the Li Diffusion in Rechargeable Battery Electrodes
journal, September 2016
- Kim, Jongsoon; Lee, Byungju; Kim, Hyungsub
- Chemistry of Materials, Vol. 28, Issue 19
Tuning the Phase Stability of Sodium Metal Pyrophosphates for Synthesis of High Voltage Cathode Materials
journal, September 2016
- Kim, Heejin; Park, Chan Sun; Choi, Jang Wook
- Chemistry of Materials, Vol. 28, Issue 18
Crystal structures of new silver ion conductors Ag7Fe3(X2O7)4 (X = P, As)
journal, January 2009
- Quarez, Eric; Mentré, Olivier; Oumellal, Yassine
- New Journal of Chemistry, Vol. 33, Issue 5
Preparation and Electrochemistry of Silver Vanadium Phosphorous Oxide, Ag[sub 2]VO[sub 2]PO[sub 4]
journal, January 2009
- Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.
- Electrochemical and Solid-State Letters, Vol. 12, Issue 1
Electrochemical Reduction of Silver Vanadium Phosphorus Oxide, Ag 2 VO 2 PO 4 : The Formation of Electrically Conductive Metallic Silver Nanoparticles
journal, October 2009
- Takeuchi, Esther S.; Marschilok, Amy C.; Tanzil, Kevin
- Chemistry of Materials, Vol. 21, Issue 20
Electrochemical reduction of silver vanadium phosphorous oxide, Ag2VO2PO4: Silver metal deposition and associated increase in electrical conductivity
journal, October 2010
- Marschilok, Amy C.; Kozarsky, Eric S.; Tanzil, Kevin
- Journal of Power Sources, Vol. 195, Issue 19
AgxVOPO4: A demonstration of the dependence of battery-related electrochemical properties of silver vanadium phosphorous oxides on Ag/V ratios
journal, March 2011
- Kim, Young Jin; Lee, Chia-Ying; Marschilok, Amy C.
- Journal of Power Sources, Vol. 196, Issue 6
Silver Vanadium Phosphorous Oxide, Ag 0.48 VOPO 4 : Exploration as a Cathode Material in Primary and Secondary Battery Applications
journal, January 2012
- Marschilok, Amy C.; Kim, Young Jin; Takeuchi, Kenneth J.
- Journal of The Electrochemical Society, Vol. 159, Issue 10
Silver vanadium diphosphate Ag2VP2O8: Electrochemistry and characterization of reduced material providing mechanistic insights
journal, April 2013
- Takeuchi, Esther S.; Lee, Chia-Ying; Cheng, Po-Jen
- Journal of Solid State Chemistry, Vol. 200
Nuclear Magnetic Resonance and X-Ray Absorption Spectroscopic Studies of Lithium Insertion in Silver Vanadium Oxide Cathodes
journal, January 2007
- Leifer, N. D.; Colon, A.; Martocci, K.
- Journal of The Electrochemical Society, Vol. 154, Issue 6
Advanced lithium batteries for implantable medical devices: mechanistic study of SVO cathode synthesis
journal, June 2003
- Takeuchi, Kenneth J.; Leising, Randolph A.; Palazzo, Marcus J.
- Journal of Power Sources, Vol. 119-121
Room Temperature Synthesis of the Larger Power, High Silver Density Cathode Material Ag 4 V 2 O 6 F 2 for Implantable Cardioverter Defibrillators
journal, June 2009
- Albrecht, Thomas A.; Sauvage, Frédéric; Bodenez, Vincent
- Chemistry of Materials, Vol. 21, Issue 13
Mild and Cost-Effective One-Pot Synthesis of Pure Single-Crystalline β-Ag0.33V2O5 Nanowires for Rechargeable Li-ion Batteries
journal, July 2011
- Hu, Wen; Zhang, Xin-bo; Cheng, Yong-liang
- ChemSusChem, Vol. 4, Issue 8
Electrochemical reduction of an Ag 2 VO 2 PO 4 particle: dramatic increase of local electronic conductivity
journal, January 2015
- Kirshenbaum, Kevin C.; Bock, David C.; Brady, Alexander B.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 17
Battery Relevant Electrochemistry of Ag 7 Fe 3 (P 2 O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+
journal, October 2016
- Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.
- Chemistry of Materials, Vol. 28, Issue 21
New insight into the working mechanism of lithium–sulfur batteries: in situ and operando X-ray diffraction characterization
journal, January 2013
- Waluś, Sylwia; Barchasz, Céline; Colin, Jean-François
- Chemical Communications, Vol. 49, Issue 72
In-situ X-ray diffraction studies of lithium–sulfur batteries
journal, March 2013
- Cañas, Natalia A.; Wolf, Steffen; Wagner, Norbert
- Journal of Power Sources, Vol. 226
In Operando X-ray Diffraction and Transmission X-ray Microscopy of Lithium Sulfur Batteries
journal, March 2012
- Nelson, Johanna; Misra, Sumohan; Yang, Yuan
- Journal of the American Chemical Society, Vol. 134, Issue 14
Insights into the Chemical Nature and Formation Mechanisms of Discharge Products in Na–O 2 Batteries by Means of Operando X-ray Diffraction
journal, April 2016
- Pinedo, R.; Weber, D. A.; Bergner, B.
- The Journal of Physical Chemistry C, Vol. 120, Issue 16
Rate-Dependent, Li-Ion Insertion/Deinsertion Behavior of LiFePO 4 Cathodes in Commercial 18650 LiFePO 4 Cells
journal, February 2014
- Liu, Qi; He, Hao; Li, Zhe-Fei
- ACS Applied Materials & Interfaces, Vol. 6, Issue 5
Direct Observation of a Metastable Crystal Phase of Li x FePO 4 under Electrochemical Phase Transition
journal, April 2013
- Orikasa, Yuki; Maeda, Takehiro; Koyama, Yukinori
- Journal of the American Chemical Society, Vol. 135, Issue 15
Irreversible phase transition between LiFePO4 and FePO4 during high-rate charge-discharge reaction by operando X-ray diffraction
journal, March 2016
- Takahashi, Ikuma; Mori, Takuya; Yoshinari, Takahiro
- Journal of Power Sources, Vol. 309
Length-Scale-Dependent Phase Transformation of LiFePO 4 : An In situ and Operando Study Using Micro-Raman Spectroscopy and XRD
journal, June 2015
- Siddique, N. A.; Salehi, Amir; Wei, Zi
- ChemPhysChem, Vol. 16, Issue 11
In operando X-ray studies of the conversion reaction in Mn 3 O 4 lithium battery anodes
journal, January 2013
- Lowe, Michael A.; Gao, Jie; Abruña, Héctor D.
- J. Mater. Chem. A, Vol. 1, Issue 6
What Happens Structurally and Electronically during the Li Conversion Reaction of CoFe 2 O 4 Nanoparticles: An Operando XAS and XRD Investigation
journal, January 2016
- Permien, Stefan; Indris, Sylvio; Schürmann, Ulrich
- Chemistry of Materials, Vol. 28, Issue 2
The Role of Reduced Graphite Oxide in Transition Metal Oxide Nanocomposites Used as Li Anode Material: An Operando Study on CoFe 2 O 4 /rGO
journal, October 2016
- Permien, Stefan; Indris, Sylvio; Neubüser, Gero
- Chemistry - A European Journal, Vol. 22, Issue 47
Study of the insertion mechanism of lithium into anatase by operando X-ray diffraction and absorption spectroscopy
journal, December 2014
- Fehse, Marcus; Monconduit, Laure; Fischer, Florent
- Solid State Ionics, Vol. 268
New Insights on the Reversible Lithiation Mechanism of TiO 2 (B) by Operando X-ray Absorption Spectroscopy and X-ray Diffraction Assisted by First-Principles Calculations
journal, November 2014
- Fehse, Marcus; Ben Yahia, Mouna; Monconduit, Laure
- The Journal of Physical Chemistry C, Vol. 118, Issue 47
In situ X-ray diffraction investigation of zinc based electrode in Ni–Zn secondary batteries
journal, October 2013
- Moser, François; Fourgeot, Fabrice; Rouget, Robert
- Electrochimica Acta, Vol. 109
Operando X-ray Studies of Crystalline Ge Anodes with Different Conductive Additives
journal, September 2015
- Lim, Linda Y.; Fan, Shufen; Hng, Huey Hoon
- The Journal of Physical Chemistry C, Vol. 119, Issue 40
In situ X-ray diffraction characterisation of Fe0.5TiOPO4 and Cu0.5TiOPO4 as electrode material for sodium-ion batteries
journal, September 2015
- Bleith, Peter; Kaiser, Hermann; Novák, Petr
- Electrochimica Acta, Vol. 176
Energy dispersive X-ray diffraction of lithium–silver vanadium phosphorous oxide cells: in situ cathode depth profiling of an electrochemical reduction–displacement reaction
journal, January 2013
- Takeuchi, Esther S.; Marschilok, Amy C.; Takeuchi, Kenneth J.
- Energy & Environmental Science, Vol. 6, Issue 5
In situ profiling of lithium/Ag2VP2O8 primary batteries using energy dispersive X-ray diffraction
journal, January 2014
- Kirshenbaum, Kevin C.; Bock, David C.; Zhong, Zhong
- Physical Chemistry Chemical Physics, Vol. 16, Issue 19, p. 9138-9147
In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism
journal, January 2015
- Kirshenbaum, K.; Bock, D. C.; Lee, C. -Y.
- Science, Vol. 347, Issue 6218
Crystal structure of the sodium ion conductor α-Na7Fe3(P2O7)4: Evidence for a long-range ordering of the Na+ ions
journal, November 1991
- Masquelier, C.; d'Yvoire, F.; Rodier, N.
- Journal of Solid State Chemistry, Vol. 95, Issue 1
A new family of sodium ion conductors: the diphosphates and diarsenates Na7M3 (X2O7)4; (M=Al, Ga, Cr, Fe; X=P, As)☆
journal, January 1994
- Masquelier, C.; Dyvoire, F.; Bretey, E.
- Solid State Ionics, Vol. 67, Issue 3-4
NIH Image to ImageJ: 25 years of image analysis
journal, June 2012
- Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W.
- Nature Methods, Vol. 9, Issue 7
Role of the PbTiO 3 Seed Layer on the Crystallization Behavior of PZT Thin Films
journal, February 2015
- Mhin, Sungwook; Nittala, Krishna; Cozzan, Clayton
- Journal of the American Ceramic Society, Vol. 98, Issue 5
In Operando Spatiotemporal Study of Li 2 O 2 Grain Growth and its Distribution Inside Operating Li-O 2 Batteries
journal, January 2014
- Shui, Jiang-Lan; Okasinski, John S.; Chen, Chen
- ChemSusChem, Vol. 7, Issue 2
Ac impedance analysis of lithium ion battery under temperature control
journal, October 2012
- Momma, Toshiyuki; Matsunaga, Mariko; Mukoyama, Daikichi
- Journal of Power Sources, Vol. 216
Using all energy in a battery
journal, January 2015
- Dudney, N. J.; Li, J.
- Science, Vol. 347, Issue 6218
Characterization of Nanoreinforcement Dispersion in Inorganic Nanocomposites: A Review
journal, May 2014
- Saheb, Nouari; Qadir, Najam; Siddiqui, Muhammad
- Materials, Vol. 7, Issue 6
Works referencing / citing this record:
DFT study of nano zinc/copper voltaic cells
journal, March 2018
- Tillman Austin, J.; Seminario, Jorge M.
- Journal of Molecular Modeling, Vol. 24, Issue 4
Lab‐Scale In Situ X‐Ray Diffraction Technique for Different Battery Systems: Designs, Applications, and Perspectives
journal, May 2019
- Xia, Maoting; Liu, Tingting; Peng, Na
- Small Methods, Vol. 3, Issue 7