Deciphering the Evolution of Current Distribution in Hybrid Silver Vanadium Oxide / Carbon Monofluoride Cathodes within Lithium Primary Batteries

Arnot, David J.; Vila, Mallory N.; Hill, Ryan C.; Kingan, Arun; Zhong, Zhong; Vo, Nghia T.; Drakopoulos, Michael; Takeuchi, Esther S.; Marschilok, Amy C.; Takeuchi, Kenneth J.

doi:10.1002/cphc.202401071

Deciphering the Evolution of Current Distribution in Hybrid Silver Vanadium Oxide / Carbon Monofluoride Cathodes within Lithium Primary Batteries

Journal Article · Wed Jan 08 00:00:00 EST 2025 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.202401071· OSTI ID:2587575

^[1]; Vila, Mallory N. ^[1]; ^[1]; ^[1]; ^[2]; Vo, Nghia T. ^[2]; Drakopoulos, Michael ^[2]; ^[3]; ^[3]; ^[3]

Stony Brook Univ., NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Stony Brook Univ., NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

For batteries to function effectively all active material must be accessible requiring both electron and ion transport to each particle. A common approach to generating the needed conductive network is the addition of carbon to create a composite electrode. An alternative approach is the electrochemically induced formation of conductive reaction products where the electrochemically generated materials are in intimate contact with the active material contributing to effective connection of each active particle. Furthermore, this study probes silver vanadium oxide (Ag₂V₄O₁₁, SVO), carbon monofluoride (CF_x), and hybrid SVO/CF_x electrodes in lithium batteries. Ex situ XRD identifies Ag⁰ as a reduction product from SVO and LiF from CF_x that can be followed as a function of depth-of-discharge (DOD). Spatially-resolved operando energy dispersive x-ray diffraction reveals that the presence of SVO alleviates reaction heterogeneity in the electrodes which are electron transfer limited in the absence of sufficient Ag⁰. Synchrotron X-ray tomography on discharged cathodes reveals the distribution of silver particles where the particles are more closely spaced near the current collector indicating multiple nucleation sites for their formation. Finally, operando isothermal microcalorimetry is used to determine the heat dissipation of the parent and hybrid battery types. Using material enthalpy potentials, we determine the current distribution between the two active materials for the discharging hybrid cathode adding further insight to the diffraction analysis. Taken together, these results provide a comprehensive understanding of hybrid SVO/CF_x cathodes and give guidance on optimal compositions that balance power and energy density considerations.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: Government of the United States; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012673; SC0012704

OSTI ID:: 2587575

Report Number(s):: BNL--228865-2025-JAAM

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 7 Vol. 26; ISSN 1439-4235; ISSN 1439-7641

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

Revisiting Discharge Mechanism of CF_x as a High Energy Density Cathode Material for Lithium Primary Battery Sayahpour, Baharak; Hirsh, Hayley; Bai, Shuang Advanced Energy Materials, Vol. 12, Issue 5 https://doi.org/10.1002/aenm.202103196	journal	December 2021
Electrochemical Activation, Sintering, and Reconstruction in Energy‐Storage Technologies: Origin, Development, and Prospects Zhang, Dongmei; Lu, Junlin; Pei, Cunyuan Advanced Energy Materials, Vol. 12, Issue 19 https://doi.org/10.1002/aenm.202103689	journal	April 2022
Discharge characteristics of silver vanadium oxide cathodes Ramasamy, R. P.; Feger, C.; Strange, T. Journal of Applied Electrochemistry, Vol. 36, Issue 4, p. 487-497 https://doi.org/10.1007/s10800-005-9103-x	journal	January 2006
Phase-transition-free rivets for layered oxide potassium cathodes Chen, Jie; Rao, Apparao M.; Gao, Caitian Nano Research, Vol. 17, Issue 11 https://doi.org/10.1007/s12274-024-6901-5	journal	August 2024
Heat dissipation from lithium/silver vanadium oxide cells during storage and low-rate discharge Bergman, G. M.; Ebel, S. J.; Takeuchi, E. S. Journal of Power Sources, Vol. 20, Issue 3-4 https://doi.org/10.1016/0378-7753(87)80109-X	journal	July 1987
Silver vanadium oxides and related battery applications Takeuchi*, K. Coordination Chemistry Reviews, Vol. 219-221 https://doi.org/10.1016/S0010-8545(01)00340-X	journal	October 2001
A measurement method for determination of dc internal resistance of batteries and supercapacitors Zhao, Shuhong; Wu, Feng; Yang, Liuxiang Electrochemistry Communications, Vol. 12, Issue 2 https://doi.org/10.1016/j.elecom.2009.12.004	journal	February 2010
Batteries used to power implantable biomedical devices Bock, David C.; Marschilok, Amy C.; Takeuchi, Kenneth J. Electrochimica Acta, Vol. 84 https://doi.org/10.1016/j.electacta.2012.03.057	journal	December 2012
Dual-chemistry cathode system for high-rate pulse applications Gan, Hong; Rubino, Robert S.; Takeuchi, Esther S. Journal of Power Sources, Vol. 146, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2005.03.203	journal	August 2005
A kinetics and equilibrium study of vanadium dissolution from vanadium oxides and phosphates in battery electrolytes: Possible impacts on ICD battery performance Bock, David C.; Marschilok, Amy C.; Takeuchi, Kenneth J. Journal of Power Sources, Vol. 231 https://doi.org/10.1016/j.jpowsour.2013.01.012	journal	June 2013
Charge transfer in Li/CFx–silver vanadium oxide hybrid cathode batteries revealed by solid state 7Li and 19F nuclear magnetic resonance spectroscopy Sideris, Paul J.; Yew, Rowena; Nieves, Ian Journal of Power Sources, Vol. 254 https://doi.org/10.1016/j.jpowsour.2013.12.108	journal	May 2014
2D Cross Sectional Analysis and Associated Electrochemistry of Composite Electrodes Containing Dispersed Agglomerates of Nanocrystalline Magnetite, Fe ₃ O ₄ Bock, David C.; Kirshenbaum, Kevin C.; Wang, Jiajun ACS Applied Materials & Interfaces, Vol. 7, Issue 24 https://doi.org/10.1021/acsami.5b02478	journal	June 2015
Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry Housel, Lisa M.; Li, Wenzao; Quilty, Calvin D. ACS Applied Materials & Interfaces, Vol. 11, Issue 41 https://doi.org/10.1021/acsami.9b10772	journal	September 2019
Solid-State Synthesis and Characterization of Silver Vanadium Oxide for Use as a Cathode Material for Lithium Batteries Leising, Randolph A.; Takeuchi, Esther Sans Chemistry of Materials, Vol. 6, Issue 4 https://doi.org/10.1021/cm00040a025	journal	April 1994
Solid-State Characterization of Reduced Silver Vanadium Oxide from the Li/SVO Discharge Reaction Leising, Randolph A.; Thiebolt, William C.; Takeuchi, Esther Sans Inorganic Chemistry, Vol. 33, Issue 25 https://doi.org/10.1021/ic00103a021	journal	December 1994
Electrochemical reduction of an Ag ₂ VO ₂ PO ₄ particle: dramatic increase of local electronic conductivity Kirshenbaum, Kevin C.; Bock, David C.; Brady, Alexander B. Physical Chemistry Chemical Physics, Vol. 17, Issue 17 https://doi.org/10.1039/C5CP00961H	journal	January 2015
Progress towards high-power Li/CF _x batteries: electrode architectures using carbon nanotubes with CF _x Zhang, Qing; Takeuchi, Kenneth J.; Takeuchi, Esther S. Physical Chemistry Chemical Physics, Vol. 17, Issue 35 https://doi.org/10.1039/C5CP03217B	journal	January 2015
Electrochemical reduction of Ag ₂ VP ₂ O ₈ composite electrodes visualized via in situ energy dispersive X-ray diffraction (EDXRD): unexpected conductive additive effects Kirshenbaum, Kevin C.; Bock, David C.; Zhong, Zhong Journal of Materials Chemistry A, Vol. 3, Issue 35 https://doi.org/10.1039/C5TA04523A	journal	January 2015
Energy dispersive X-ray diffraction (EDXRD) for operando materials characterization within batteries Marschilok, Amy C.; Bruck, Andrea M.; Abraham, Alyson Physical Chemistry Chemical Physics, Vol. 22, Issue 37 https://doi.org/10.1039/D0CP00778A	journal	January 2020
Silver vanadium oxide and silver vanadium phosphorous oxide dissolution kinetics: a mechanistic study with possible impact on future ICD battery lifetimes Bock, David C.; Takeuchi, Kenneth J.; Marschilok, Amy C. Dalton Transactions, Vol. 42, Issue 38 https://doi.org/10.1039/c3dt51544c	journal	January 2013
Crystal structure and electronic properties of the Ag ₂ V ₄ O ₁₁ insertion electrode Onoda, Masashige; Kanbe, Keisuke Journal of Physics: Condensed Matter, Vol. 13, Issue 31 https://doi.org/10.1088/0953-8984/13/31/308	journal	July 2001
In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism Kirshenbaum, K.; Bock, D. C.; Lee, C. -Y. Science, Vol. 347, Issue 6218 https://doi.org/10.1126/science.1257289	journal	January 2015
Using all energy in a battery Dudney, N. J.; Li, J. Science, Vol. 347, Issue 6218 https://doi.org/10.1126/science.aaa2870	journal	January 2015
The Reduction of Silver Vanadium Oxide in Lithium/Silver Vanadium Oxide Cells Takeuchi, Esther Sans; Thiebolt III, William C. Journal of The Electrochemical Society, Vol. 135, Issue 11, p. 2691-2694 https://doi.org/10.1149/1.2095412	journal	January 1988
Mechanism of Reduction of the Fluorographite Cathode Whittingham, M. Stanley Journal of The Electrochemical Society, Vol. 122, Issue 4 https://doi.org/10.1149/1.2134252	journal	January 1975
Modeling Li∕CF[sub x]-SVO Hybrid-Cathode Batteries Gomadam, Parthasarathy M.; Merritt, Donald R.; Scott, Erik R. Journal of The Electrochemical Society, Vol. 154, Issue 11 https://doi.org/10.1149/1.2779963	journal	January 2007
Mathematical Modeling of Li/CFx-SVO Batteries Gomadam, Parthasarathy; Merritt, Donald; Scott, Erik ECS Transactions, Vol. 3, Issue 36 https://doi.org/10.1149/1.2795105	journal	September 2007
Preparation and Electrochemistry of Silver Vanadium Phosphorous Oxide, Ag[sub 2]VO[sub 2]PO[sub 4] Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S. Electrochemical and Solid-State Letters, Vol. 12, Issue 1 https://doi.org/10.1149/1.2998546	journal	January 2009
Isothermal Microcalorimetric Analysis of Li/CF_x Battery Discharge Arnot, David J.; Takeuchi, Esther S.; Marschilok, Amy C. Journal of The Electrochemical Society, Vol. 170, Issue 6 https://doi.org/10.1149/1945-7111/acd813	journal	June 2023
Modeling a High-Energy, High-Rate Li//CFx Battery with a Capacity-Contributing Electrolyte Parke, Caitlin D.; Harris, Kailot C.; Zhang, Xiyue Journal of The Electrochemical Society, Vol. 171, Issue 7 https://doi.org/10.1149/1945-7111/ad63cc	journal	July 2024
Rate Dependent Multi-Mechanism Discharge of Ag _0.50 VOPO ₄ ·1.8H ₂ O: Insights from In Situ Energy Dispersive X-ray Diffraction Huie, Matthew M.; Bock, David C.; Zhong, Zhong Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0011701jes	journal	September 2016
Tomographic 3D Analysis of Reduction Displacement Reaction with Associated Formation of a Conductive Network in High Energy Primary Batteries Bruck, Andrea M.; Li, Yue Ru; Brady, Alexander B. Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.0411914jes	journal	January 2019
Pulse Polarization for Li-Ion Battery under Constant State of Charge: Part I. Pulse Discharge Experiments DuBeshter, Tyler; Jorne, Jacob Journal of The Electrochemical Society, Vol. 164, Issue 11 https://doi.org/10.1149/2.0551711jes	journal	January 2017
Hybrid Ag ₂ VO ₂ PO ₄ /CF _x as a High Capacity and Energy Cathode for Primary Batteries Li, Yue Ru; Bruck, Andrea M.; Brady, Alexander B. Journal of The Electrochemical Society, Vol. 164, Issue 12 https://doi.org/10.1149/2.0991712jes	journal	January 2017
Data processing methods and data acquisition for samples larger than the field of view in parallel-beam tomography Vo, Nghia T.; Atwood, Robert C.; Drakopoulos, Michael Optics Express, Vol. 29, Issue 12 https://doi.org/10.1364/OE.418448	journal	May 2021