The energetics of phosphoric acid interactions reveals a new acid loss mechanism
Abstract
Acid retention of phosphoric acid (PA)-doped proton exchange membranes (PEMs) is one of the critical factors that determine the durability of high temperature PEM fuel cells. However, the mechanism of PA loss in the PEMs in the presence of water is obscure in the context of the energetics of the PA cluster. Here, we study the energetics of PA-benzimidazole acid-base and biphosphate-ammonium ion pairs using density functional theory calculations and 31P NMR experiments to propose a novel PA loss mechanism. The results suggest that the removal of the PA from the membrane does not occur due to the strong interaction of PA-water, but due to the incapability of the base polymers to hold the water and PA beyond a certain level. Significantly higher interaction in the biphosphate-ammonium ion pair shifts the equilibrium PA composition in the PA cluster to higher values, which minimizes the PA loss in the presence of water. Introducing the high interaction with PA molecules provides a path for better PEM design that may allow using high temperature PEM fuel cells with excellent acid retention.
- Authors:
-
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of New Mexico, Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1526963
- Alternate Identifier(s):
- OSTI ID: 1504509
- Report Number(s):
- LA-UR-18-31799
Journal ID: ISSN 2050-7488; JMCAET
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 16; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Energy Sciences
Citation Formats
Lee, Albert S., Choe, Yoong-Kee, Matanovic, Ivana, and Kim, Yu Seung. The energetics of phosphoric acid interactions reveals a new acid loss mechanism. United States: N. p., 2019.
Web. doi:10.1039/C9TA01756A.
Lee, Albert S., Choe, Yoong-Kee, Matanovic, Ivana, & Kim, Yu Seung. The energetics of phosphoric acid interactions reveals a new acid loss mechanism. United States. https://doi.org/10.1039/C9TA01756A
Lee, Albert S., Choe, Yoong-Kee, Matanovic, Ivana, and Kim, Yu Seung. Mon .
"The energetics of phosphoric acid interactions reveals a new acid loss mechanism". United States. https://doi.org/10.1039/C9TA01756A. https://www.osti.gov/servlets/purl/1526963.
@article{osti_1526963,
title = {The energetics of phosphoric acid interactions reveals a new acid loss mechanism},
author = {Lee, Albert S. and Choe, Yoong-Kee and Matanovic, Ivana and Kim, Yu Seung},
abstractNote = {Acid retention of phosphoric acid (PA)-doped proton exchange membranes (PEMs) is one of the critical factors that determine the durability of high temperature PEM fuel cells. However, the mechanism of PA loss in the PEMs in the presence of water is obscure in the context of the energetics of the PA cluster. Here, we study the energetics of PA-benzimidazole acid-base and biphosphate-ammonium ion pairs using density functional theory calculations and 31P NMR experiments to propose a novel PA loss mechanism. The results suggest that the removal of the PA from the membrane does not occur due to the strong interaction of PA-water, but due to the incapability of the base polymers to hold the water and PA beyond a certain level. Significantly higher interaction in the biphosphate-ammonium ion pair shifts the equilibrium PA composition in the PA cluster to higher values, which minimizes the PA loss in the presence of water. Introducing the high interaction with PA molecules provides a path for better PEM design that may allow using high temperature PEM fuel cells with excellent acid retention.},
doi = {10.1039/C9TA01756A},
journal = {Journal of Materials Chemistry. A},
number = 16,
volume = 7,
place = {United States},
year = {Mon Mar 18 00:00:00 EDT 2019},
month = {Mon Mar 18 00:00:00 EDT 2019}
}
Web of Science
Works referenced in this record:
Polymer membranes for high temperature proton exchange membrane fuel cell: Recent advances and challenges
journal, June 2011
- Bose, Saswata; Kuila, Tapas; Nguyen, Thi Xuan Hien
- Progress in Polymer Science, Vol. 36, Issue 6
The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells
journal, March 2016
- Kongkanand, Anusorn; Mathias, Mark F.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
Experimental investigation and numerical simulation of the electrolyte loss in a HT-PEM fuel cell
journal, January 2015
- Lang, Sebastian; Kazdal, Timur J.; Kühl, Frank
- International Journal of Hydrogen Energy, Vol. 40, Issue 2
State of Water in Disulfonated Poly(arylene ether sulfone) Copolymers and a Perfluorosulfonic Acid Copolymer (Nafion) and Its Effect on Physical and Electrochemical Properties
journal, August 2003
- Kim, Yu Seung; Dong, Limin; Hickner, Michael A.
- Macromolecules, Vol. 36, Issue 17
Long-Term Durability of PBI-Based HT-PEM Fuel Cells: Effect of Operating Parameters
journal, January 2018
- Søndergaard, Tonny; Cleemann, Lars Nilausen; Becker, Hans
- Journal of The Electrochemical Society, Vol. 165, Issue 6
Phosphoric acid doped hydrophobic ionic liquid-based composite membranes for anhydrous proton exchange membrane application
journal, January 2017
- Lin, Bencai; Qiao, Gang; Chu, Fuqiang
- RSC Advances, Vol. 7, Issue 2
Effects of mesoporous fillers on properties of polybenzimidazole composite membranes for high-temperature polymer fuel cells
journal, March 2018
- Kuo, Ying-Jeng; Lin, Hsiu-Li
- International Journal of Hydrogen Energy, Vol. 43, Issue 9
Infrared Spectroscopy of Polybenzimidazole in the Dry and Hydrate Forms: A Combined Experimental and Computational Study
journal, September 2018
- Musto, Pellegrino; La Manna, Pietro; Moon, Joshua D.
- ACS Omega, Vol. 3, Issue 9
Correlating Electrolyte Inventory and Lifetime of HT-PEFC by Accelerated Stress Testing
journal, January 2015
- Eberhardt, S. H.; Lochner, T.; Büchi, F. N.
- Journal of The Electrochemical Society, Vol. 162, Issue 12
Interplay between structure and properties in acid-base blend PBI-based membranes for HT-PEM fuel cells
journal, August 2017
- Giffin, Guinevere A.; Galbiati, Samuele; Walter, Mario
- Journal of Membrane Science, Vol. 535
Fitting the Coulomb potential variationally in Xα molecular calculations
journal, March 1983
- Dunlap, B. I.
- The Journal of Chemical Physics, Vol. 78, Issue 6
Cross-Linkable Polymeric Ionic Liquid Improve Phosphoric Acid Retention and Long-Term Conductivity Stability in Polybenzimidazole Based PEMs
journal, November 2018
- Liu, Fengxiang; Wang, Shuang; Chen, Hao
- ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 12
Demonstration of a 20 W class high-temperature polymer electrolyte fuel cell stack with novel fabrication of a membrane electrode assembly
journal, May 2011
- Lee, Hye-Jin; Kim, Byoung Gak; Lee, Dong Hoon
- International Journal of Hydrogen Energy, Vol. 36, Issue 9
Quaternized aryl ether-free polyaromatics for alkaline membrane fuel cells: synthesis, properties, and performance – a topical review
journal, January 2018
- Park, Eun Joo; Kim, Yu Seung
- Journal of Materials Chemistry A, Vol. 6, Issue 32
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC) – A review
journal, June 2013
- Chandan, Amrit; Hattenberger, Mariska; El-kharouf, Ahmad
- Journal of Power Sources, Vol. 231
Low acid leaching PEM for fuel cell based on polybenzimidazole nanocomposites with protic ionic liquid modified silica
journal, June 2015
- Maity, Sudhangshu; Singha, Shuvra; Jana, Tushar
- Polymer, Vol. 66
Durability Studies of PBI‐based High Temperature PEMFCs
journal, July 2008
- Yu, S.; Xiao, L.; Benicewicz, B. C.
- Fuel Cells, Vol. 8, Issue 3‒4
Degradation in phosphoric acid doped polymer fuel cells: A 6000 h parametric investigation
journal, May 2013
- Galbiati, Samuele; Baricci, Andrea; Casalegno, Andrea
- International Journal of Hydrogen Energy, Vol. 38, Issue 15
Durability of ABPBI-based MEAs for High Temperature PEMFCs at Different Operating Conditions
journal, April 2008
- Wannek, C.; Kohnen, B.; Oetjen, H. -F.
- Fuel Cells, Vol. 8, Issue 2
On the conductivity of phosphoric acid electrolyte
journal, January 1989
- Chin, Der-Tau; Chang, Howard H.
- Journal of Applied Electrochemistry, Vol. 19, Issue 1
Polybenzimidazole gel membrane for the use in fuel cell
journal, September 2011
- Sannigrahi, Arindam; Ghosh, Sandip; Maity, Sudhangshu
- Polymer, Vol. 52, Issue 19
A polybenzimidazole/sulfonated graphite oxide composite membrane for high temperature polymer electrolyte membrane fuel cells
journal, January 2011
- Xu, Chenxi; Cao, Yuancheng; Kumar, Ravi
- Journal of Materials Chemistry, Vol. 21, Issue 30
Hydrogen bonds in complexes of phosphonic and metylphosphonic acids with dimethylformamide
journal, November 2015
- Khatuntseva, E. A.; Krest’yaninov, M. A.; Fedorova, I. V.
- Russian Journal of Physical Chemistry A, Vol. 89, Issue 12
Acid Absorbancy of an Electrode and Its Cell Performance History
journal, January 1988
- Mori, T.
- Journal of The Electrochemical Society, Vol. 135, Issue 5
Study of the influence of the amount of PBI–H3PO4 in the catalytic layer of a high temperature PEMFC
journal, February 2010
- Lobato, Justo; Cañizares, Pablo; Rodrigo, Manuel A.
- International Journal of Hydrogen Energy, Vol. 35, Issue 3
Ab Initio Modeling of Proton Transfer in Phosphoric Acid Clusters
journal, August 2009
- Vilciauskas, Linas; Paddison, Stephen J.; Kreuer, Klaus-Dieter
- The Journal of Physical Chemistry A, Vol. 113, Issue 32
Water sorption, desorption and transport in Nafion membranes
journal, September 2007
- Majsztrik, Paul W.; Satterfield, M. Barclay; Bocarsly, Andrew B.
- Journal of Membrane Science, Vol. 301, Issue 1-2
Water uptake and acid doping of polybenzimidazoles as electrolyte membranes for fuel cells
journal, March 2004
- Li, Q.
- Solid State Ionics, Vol. 168, Issue 1-2
Polybenzimidazole-Based Membranes as a Real Alternative to Nafion for Fuel Cells Operating at Low Temperature
journal, April 2008
- Mustarelli, Piercarlo; Quartarone, Eliana; Grandi, Stefania
- Advanced Materials, Vol. 20, Issue 7
High temperature proton exchange membranes based on polybenzimidazoles for fuel cells
journal, May 2009
- Li, Qingfeng; Jensen, Jens Oluf; Savinell, Robert F.
- Progress in Polymer Science, Vol. 34, Issue 5
Quantum-chemical studies of dimethylformamide 1 : 1 complexes with phosphoric acid
journal, October 2012
- Krest’yaninov, M. A.; Kiselev, M. G.; Safonova, L. P.
- Russian Journal of Physical Chemistry A, Vol. 86, Issue 12
Polybenzimidazole based nanocomposite membranes with enhanced proton conductivity for high temperature PEM fuel cells
journal, January 2017
- Özdemir, Yağmur; Üregen, Nurhan; Devrim, Yılser
- International Journal of Hydrogen Energy, Vol. 42, Issue 4
Robust and variational fitting: Removing the four-center integrals from center stage in quantum chemistry
journal, September 2000
- Dunlap, B. I.
- Journal of Molecular Structure: THEOCHEM, Vol. 529, Issue 1-3
Fuel cell systems for transportation: Status and trends
journal, February 2008
- Ahluwalia, Rajesh K.; Wang, Xiaohua.
- Journal of Power Sources, Vol. 177, Issue 1
Alkaline stability of poly(phenylene)-based anion exchange membranes with various cations
journal, August 2012
- Hibbs, Michael R.; Hickner, Michael A.; Coughlin, E. Bryan
- Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 24, p. 1736-1742
Scale-up of a high temperature polymer electrolyte membrane fuel cell based on polybenzimidazole
journal, May 2011
- Pinar, F. Javier; Cañizares, Pablo; Rodrigo, Manuel A.
- Journal of Power Sources, Vol. 196, Issue 9
Water Sorption, Desorption and Transport in Nafion Membranes
journal, September 2007
- Majsztrik, Paul; Satterfield, Barclay; Bocarsly, Andrew
- ECS Transactions, Vol. 11, Issue 1
Water Sorption, Desorption and Transport in Nafion Membranes
journal, September 2007
- Majsztrik, Paul; Satterfield, Barclay; Bocarsly, Andrew
- ECS Meeting Abstracts, Vol. MA2007-02, Issue 9