Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes

Bui, Justin C.; Digdaya, Ibadillah; Xiang, Chengxiang; Bell, Alexis T.; Weber, Adam Z.

doi:10.1021/acsami.0c12686

Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes

Journal Article · Tue Nov 10 04:00:00 EST 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c12686· OSTI ID:1828548

^[1]; Digdaya, Ibadillah ^[2]; ^[2]; ^[1]; ^[3]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Bipolar membranes (BPMs) have the potential to become critical components in electrochemical devices for a variety of electrolysis and electrosynthesis applications. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-electrolyzers. In this study, a continuum model of multi-ion transport in a BPM is developed and fit to experimental data. Specifically, concentration profiles are determined for all ionic species, and the importance of a water-dissociation catalyst is demonstrated. The model describes internal concentration polarization and co- and counter-ion crossover in BPMs, determining the mode of transport for ions within the BPM and revealing the significance of salt-ion crossover when operated with pH gradients relevant to electrolysis and electrosynthesis. Lastly, a sensitivity analysis reveals that the performance and lifetime of BPMs can be improved substantially by using of thinner dissociation catalysts, managing water transport, modulating the thickness of the individual layers in the BPM to control salt-ion crossover, and increasing the ion-exchange capacity of the ion-exchange layers in order to amplify the water-dissociation kinetics at the interface.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1828548

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 47 Vol. 12; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Electrochemical characterization of polymer ion‐exchange bipolar membranes Mafé, S.; Ramírez, P. Acta Polymerica, Vol. 48, Issue 7, p. 234-250 https://doi.org/10.1002/actp.1997.010480702	journal	July 1997
Bipolar Membrane-Assisted Solar Water Splitting in Optimal pH Luo, Jingshan; Vermaas, David A.; Bi, Dongqin Advanced Energy Materials, Vol. 6, Issue 13 https://doi.org/10.1002/aenm.201600100	journal	April 2016
A Stabilized, Intrinsically Safe, 10% Efficient, Solar-Driven Water-Splitting Cell Incorporating Earth-Abundant Electrocatalysts with Steady-State pH Gradients and Product Separation Enabled by a Bipolar Membrane Sun, Ke; Liu, Rui; Chen, Yikai Advanced Energy Materials, Vol. 6, Issue 13 https://doi.org/10.1002/aenm.201600379	journal	April 2016
Proton Transfer, Acid-Base Catalysis, and Enzymatic Hydrolysis. Part I: ELEMENTARY PROCESSES Eigen, M. Angewandte Chemie International Edition in English, Vol. 3, Issue 1 https://doi.org/10.1002/anie.196400011	journal	January 1964
Effects of Anion Identity and Concentration on Electrochemical Reduction of CO ₂ Resasco, Joaquin; Lum, Yanwei; Clark, Ezra ChemElectroChem, Vol. 5, Issue 7 https://doi.org/10.1002/celc.201701316	journal	February 2018
Use of Bipolar Membranes for Maintaining Steady-State pH Gradients in Membrane-Supported, Solar-Driven Water Splitting McDonald, Michael B.; Ardo, Shane; Lewis, Nathan S. ChemSusChem, Vol. 7, Issue 11 https://doi.org/10.1002/cssc.201402288	journal	September 2014
Reduced Graphene Oxide Bipolar Membranes for Integrated Solar Water Splitting in Optimal pH McDonald, Michael B.; Bruce, Jared P.; McEleney, Kevin ChemSusChem, Vol. 8, Issue 16 https://doi.org/10.1002/cssc.201500538	journal	July 2015
Catalytic, Conductive Bipolar Membrane Interfaces through Layer-by-Layer Deposition for the Design of Membrane-Integrated Artificial Photosynthesis Systems McDonald, Michael B.; Freund, Michael S.; Hammond, Paula T. ChemSusChem, Vol. 10, Issue 22 https://doi.org/10.1002/cssc.201701397	journal	November 2017
Sustainion Imidazolium-Functionalized Polymers for Carbon Dioxide Electrolysis Kutz, Robert B.; Chen, Qingmei; Yang, Hongzhou Energy Technology, Vol. 5, Issue 6 https://doi.org/10.1002/ente.201600636	journal	March 2017
Electric field-assisted proton transfer and water dissociation at the junction of a fixed-charge bipolar membrane Mafé, Salvador; Ramı́rez, Patricio; Alcaraz, Antonio Chemical Physics Letters, Vol. 294, Issue 4-5 https://doi.org/10.1016/S0009-2614(98)00877-X	journal	September 1998
Electro-catalytic membrane reactors and the development of bipolar membrane technology Balster, J.; Stamatialis, D. F.; Wessling, M. Chemical Engineering and Processing: Process Intensification, Vol. 43, Issue 9 https://doi.org/10.1016/j.cep.2003.11.010	journal	September 2004
Transport phenomena in flow battery ion-conducting membranes Kushner, Douglas I.; Crothers, Andrew R.; Kusoglu, Ahmet Current Opinion in Electrochemistry, Vol. 21 https://doi.org/10.1016/j.coelec.2020.01.010	journal	June 2020
Conversion of Visible Light into Ionic Power Using Photoacid-Dye-Sensitized Bipolar Ion-Exchange Membranes White, William; Sanborn, Christopher D.; Fabian, David M. Joule, Vol. 2, Issue 1 https://doi.org/10.1016/j.joule.2017.10.015	journal	January 2018
Effect of CO 2 absorption on ion and water mobility in an anion exchange membrane Peng, Jing; Roy, Asa L.; Greenbaum, Steve G. Journal of Power Sources, Vol. 380 https://doi.org/10.1016/j.jpowsour.2018.01.071	journal	March 2018
Experimental and theoretical investigations of steady and transient states in systems of ion exchange bipolar membranes Hurwitz, H. D.; Dibiani, R. Journal of Membrane Science, Vol. 228, Issue 1 https://doi.org/10.1016/j.memsci.2003.09.009	journal	January 2004
Ionic transport through ion-exchange and bipolar membranes Volgin, V. M.; Davydov, A. D. Journal of Membrane Science, Vol. 259, Issue 1-2 https://doi.org/10.1016/j.memsci.2005.03.010	journal	August 2005
Proton exchange membrane for DMFC and H2/air fuel cells: Synthesis and characterization of partially fluorinated disulfonated poly(arylene ether benzonitrile) copolymers Sankir, M.; Kim, Yu Seung; Pivovar, Bryan S. Journal of Membrane Science, Vol. 299, Issue 1-2 https://doi.org/10.1016/j.memsci.2007.04.004	journal	August 2007
A comprehensive mathematical model of water splitting in bipolar membranes: Impact of the spatial distribution of fixed charges and catalyst at bipolar junction Mareev, S. A.; Evdochenko, E.; Wessling, M. Journal of Membrane Science, Vol. 603 https://doi.org/10.1016/j.memsci.2020.118010	journal	May 2020
PEM electrolysis for production of hydrogen from renewable energy sources Barbir, Frano Solar Energy, Vol. 78, Issue 5 https://doi.org/10.1016/j.solener.2004.09.003	journal	May 2005
The role of internal pressure for the hydration and transport properties of ionomers and polyelectrolytes Kreuer, Klaus-Dieter Solid State Ionics, Vol. 252 https://doi.org/10.1016/j.ssi.2013.04.018	journal	December 2013
Organic Electrosynthesis for Sustainable Chemical Manufacturing Blanco, Daniela E.; Modestino, Miguel A. Trends in Chemistry, Vol. 1, Issue 1 https://doi.org/10.1016/j.trechm.2019.01.001	journal	April 2019
New Insights into Perfluorinated Sulfonic-Acid Ionomers Kusoglu, Ahmet; Weber, Adam Z. Chemical Reviews, Vol. 117, Issue 3 https://doi.org/10.1021/acs.chemrev.6b00159	journal	January 2017
Inherent Acidity of Perfluorosulfonic Acid Ionomer Dispersions and Implications for Ink Aggregation Berlinger, Sarah A.; McCloskey, Bryan D.; Weber, Adam Z. The Journal of Physical Chemistry B, Vol. 122, Issue 31 https://doi.org/10.1021/acs.jpcb.8b06493	journal	July 2018
Reduced Ion Crossover in Bipolar Membrane Electrolysis via Increased Current Density, Molecular Size, and Valence Blommaert, Marijn A.; Verdonk, Joost A. H.; Blommaert, Hester C. B. ACS Applied Energy Materials, Vol. 3, Issue 6 https://doi.org/10.1021/acsaem.0c00687	journal	May 2020
Analysis of Mass Flows and Membrane Cross-over in CO ₂ Reduction at High Current Densities in an MEA-Type Electrolyzer Larrazábal, Gastón O.; Strøm-Hansen, Patrick; Heli, Jens P. ACS Applied Materials & Interfaces, Vol. 11, Issue 44 https://doi.org/10.1021/acsami.9b13081	journal	October 2019
Electrolysis of CO ₂ to Syngas in Bipolar Membrane-Based Electrochemical Cells Li, Yuguang C.; Zhou, Dekai; Yan, Zhifei ACS Energy Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsenergylett.6b00475	journal	November 2016
Synergistic Electrochemical CO ₂ Reduction and Water Oxidation with a Bipolar Membrane Vermaas, David A.; Smith, Wilson A. ACS Energy Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsenergylett.6b00557	journal	November 2016
Ionic Processes in Water Electrolysis: The Role of Ion-Selective Membranes Oener, S. Z.; Ardo, S.; Boettcher, S. W. ACS Energy Letters, Vol. 2, Issue 11 https://doi.org/10.1021/acsenergylett.7b00764	journal	October 2017
Electrolysis of Gaseous CO ₂ to CO in a Flow Cell with a Bipolar Membrane Salvatore, Danielle A.; Weekes, David M.; He, Jingfu ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b01017	journal	November 2017
Graphene Oxide as a Water Dissociation Catalyst in the Bipolar Membrane Interfacial Layer McDonald, Michael B.; Freund, Michael S. ACS Applied Materials & Interfaces, Vol. 6, Issue 16 https://doi.org/10.1021/am503242v	journal	July 2014
Transport in Proton Conductors for Fuel-Cell Applications: Simulations, Elementary Reactions, and Phenomenology Kreuer, Klaus-Dieter; Paddison, Stephen J.; Spohr, Eckhard Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020715f	journal	October 2004
Recombination of hydrogen ion (H+) and hydroxide in pure liquid water Natzle, Wesley C.; Moore, C. Bradley The Journal of Physical Chemistry, Vol. 89, Issue 12 https://doi.org/10.1021/j100258a035	journal	June 1985
Irreversible Processes in Electrolytes. Diffusion, Conductance and Viscous Flow in Arbitrary Mixtures of Strong Electrolytes Onsager, Lars; Fuoss, R. M. The Journal of Physical Chemistry, Vol. 36, Issue 11 https://doi.org/10.1021/j150341a001	journal	November 1932
Dielectric Constant for the Dioxane—Water System from 20 to 35° Critchfield, Frank E.; Gibson, John A.; Hall, James L. Journal of the American Chemical Society, Vol. 75, Issue 8 https://doi.org/10.1021/ja01104a506	journal	April 1953
Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M. Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/ja510442p	journal	March 2015
Proton Transfer and Proton Concentrations in Protonated Nafion Fuel Cell Membranes Spry, D. B.; Fayer, M. D. The Journal of Physical Chemistry B, Vol. 113, Issue 30 https://doi.org/10.1021/jp9036777	journal	July 2009
Acidity and catalytic activity of Nafion-H Sondheimer, Susan J.; Bunce, Nigel J.; Lemke, Mary E. Macromolecules, Vol. 19, Issue 2 https://doi.org/10.1021/ma00156a016	journal	March 1986
Onsager’s Wien effect on a lattice Kaiser, V.; Bramwell, S. T.; Holdsworth, P. C. W. Nature Materials, Vol. 12, Issue 11 https://doi.org/10.1038/nmat3729	journal	August 2013
Non-aqueous gas diffusion electrodes for rapid ammonia synthesis from nitrogen and water-splitting-derived hydrogen Lazouski, Nikifar; Chung, Minju; Williams, Kindle Nature Catalysis, Vol. 3, Issue 5 https://doi.org/10.1038/s41929-020-0455-8	journal	May 2020
Solar hydrogen production from seawater vapor electrolysis Kumari, Sudesh; Turner White, R.; Kumar, Bijandra Energy & Environmental Science, Vol. 9, Issue 5 https://doi.org/10.1039/C5EE03568F	journal	January 2016
Ion diode logics for pH control Gabrielsson, Erik O.; Tybrandt, Klas; Berggren, Magnus Lab on a Chip, Vol. 12, Issue 14 https://doi.org/10.1039/c2lc40093f	journal	January 2012
A comparative technoeconomic analysis of renewable hydrogen production using solar energy Shaner, Matthew R.; Atwater, Harry A.; Lewis, Nathan S. Energy & Environmental Science, Vol. 9, Issue 7 https://doi.org/10.1039/c5ee02573g	journal	January 2016
Photo-assisted water splitting with bipolar membrane induced pH gradients for practical solar fuel devices Vermaas, David A.; Sassenburg, Mark; Smith, Wilson A. Journal of Materials Chemistry A, Vol. 3, Issue 38 https://doi.org/10.1039/c5ta06315a	journal	January 2015
Principles and implementations of electrolysis systems for water splitting Xiang, Chengxiang; Papadantonakis, Kimberly M.; Lewis, Nathan S. Materials Horizons, Vol. 3, Issue 3 https://doi.org/10.1039/c6mh00016a	journal	January 2016
High performance electrospun bipolar membrane with a 3D junction Shen, Chunhui; Wycisk, Ryszard; Pintauro, Peter N. Energy & Environmental Science, Vol. 10, Issue 6 https://doi.org/10.1039/c7ee00345e	journal	January 2017
The balance of electric field and interfacial catalysis in promoting water dissociation in bipolar membranes Yan, Zhifei; Zhu, Liang; Li, Yuguang C. Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/c8ee01192c	journal	January 2018
Enhancing selectivity and efficiency in the electrochemical synthesis of adiponitrile Blanco, Daniela E.; Dookhith, Aaliyah Z.; Modestino, Miguel A. Reaction Chemistry & Engineering, Vol. 4, Issue 1 https://doi.org/10.1039/c8re00262b	journal	January 2019
Ion transport mechanisms in bipolar membranes for (photo)electrochemical water splitting Vermaas, David A.; Wiegman, Sandra; Nagaki, Tetsuro Sustainable Energy & Fuels, Vol. 2, Issue 9 https://doi.org/10.1039/c8se00118a	journal	January 2018
Towards membrane-electrode assembly systems for CO ₂ reduction: a modeling study Weng, Lien-Chun; Bell, Alexis T.; Weber, Adam Z. Energy & Environmental Science, Vol. 12, Issue 6 https://doi.org/10.1039/c9ee00909d	journal	January 2019
Insights into membrane-separated organic electrosynthesis: the case of adiponitrile electrochemical production Blanco, Daniela E.; Prasad, Purnima A.; Dunningan, Kaylee Reaction Chemistry & Engineering, Vol. 5, Issue 1 https://doi.org/10.1039/c9re00389d	journal	January 2020
A review on electrocatalytic oxidation of methane to oxygenates Bagherzadeh Mostaghimi, Amir Hassan; Al-Attas, Tareq A.; Kibria, Md Golam Journal of Materials Chemistry A, Vol. 8, Issue 31 https://doi.org/10.1039/d0ta03758c	journal	January 2020
Current‐voltage curves of bipolar membranes Ramírez, P.; Rapp, H. J.; Reichle, S. Journal of Applied Physics, Vol. 72, Issue 1 https://doi.org/10.1063/1.352124	journal	July 1992
Modeling proton-exchange-membrane fuel cell performance/degradation tradeoffs with chemical scavengers Ehlinger, Victoria M.; Crothers, Andrew R.; Kusoglu, Ahmet Journal of Physics: Energy, Vol. 2, Issue 4 https://doi.org/10.1088/2515-7655/abb194	journal	October 2020
Accelerating water dissociation in bipolar membranes and for electrocatalysis Oener, Sebastian Z.; Foster, Marc J.; Boettcher, Shannon W. Science, Vol. 369, Issue 6507 https://doi.org/10.1126/science.aaz1487	journal	July 2020
A Study of Carbonate Formation Kinetics and Morphological Effects Observed on OH ^- Form of Pfaem When Exposed to Air Containing CO ₂ Divekar, Ashutosh G.; Park, Andrew Michael; Owczarczyk, Zbyslaw R. ECS Transactions, Vol. 80, Issue 8 https://doi.org/10.1149/08008.1005ecst	journal	August 2017
Transport in Polymer-Electrolyte Membranes Weber, Adam Z.; Newman, John Journal of The Electrochemical Society, Vol. 151, Issue 2 https://doi.org/10.1149/1.1639157	journal	January 2004
Thermodynamics and Proton Transport in Nafion Choi, Pyoungho; Jalani, Nikhil H.; Datta, Ravindra Journal of The Electrochemical Society, Vol. 152, Issue 3 https://doi.org/10.1149/1.1859814	journal	January 2005
A Dusty Fluid Model for Predicting Hydroxyl Anion Conductivity in Alkaline Anion Exchange Membranes Grew, Kyle N.; Chiu, Wilson K. S. Journal of The Electrochemical Society, Vol. 157, Issue 3 https://doi.org/10.1149/1.3273200	journal	January 2010
Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part I. Thermodynamic Model and Validation Crothers, Andrew R.; Darling, Robert M.; Kusoglu, Ahmet Journal of The Electrochemical Society, Vol. 167, Issue 1 https://doi.org/10.1149/1945-7111/ab6723	journal	January 2020
Effects of Temperature and Carbon Dioxide on Anion Exchange Membrane Conductivity Grew, Kyle N.; Ren, Xiaoming; Chu, Deryn Electrochemical and Solid-State Letters, Vol. 14, Issue 12 https://doi.org/10.1149/2.011112esl	journal	January 2011
Design Principles of Bipolar Electrochemical Co-Electrolysis Cells for Efficient Reduction of Carbon Dioxide from Gas Phase at Low Temperature Pătru, Alexandra; Binninger, Tobias; Pribyl, Bernhard Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.1221816jes	journal	January 2019

Similar Records

(Invited) Understanding Multi-Component Transport and Reaction Phenomena in Bipolar Membranes Used for Electrosynthesis

Journal Article · Sun May 30 00:00:00 EDT 2021 · ECS Meeting Abstracts · OSTI ID:1866782

Ion-specific phenomena limit energy recovery in forward-biased bipolar membranes

Journal Article · Thu Dec 19 23:00:00 EST 2024 · Nature Chemical Engineering · OSTI ID:2565274

On the Nature of Field-Enhanced Water Dissociation in Bipolar Membranes

Journal Article · Mon Nov 08 23:00:00 EST 2021 · Journal of Physical Chemistry. C · OSTI ID:1897718

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction
bipolar membrane
electrochemistry
electrolysis
ionomers
model
transport
water splitting

Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes

Citation Formats

References (61)

Similar Records

Related Subjects