An Interfacial Engineering Approach toward Operation of a Porous Solid Electrolyte CO2 Electrolyzer

Cherniack, Luke H.; Hansen, Kentaro U.; Li, Zoushuang; Taylor, Audrey K.; Neyerlin, Kenneth C.; Jiao, Feng

doi:10.1021/acsenergylett.5c00079

Title: An Interfacial Engineering Approach toward Operation of a Porous Solid Electrolyte CO₂ Electrolyzer

Journal Article · Wed Mar 05 00:00:00 UTC 2025 · ACS Energy Letters

DOI: https://doi.org/10.1021/acsenergylett.5c00079 · OSTI ID:2549272

^[1];

^[1]; Li, Zoushuang ^[2];

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Univ. of Delaware, Newark, DE (United States)
Washington Univ., St. Louis, MO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Waste CO₂ can be repurposed as a carbon feedstock for synthesizing valuable chemicals via CO₂ electrolysis. Porous solid electrolyte (PSE) CO₂ electrolysis has been demonstrated as an economically viable method to produce high purity products. This work applies an interfacial engineering approach to determine key factors to improve performance in PSE CO₂ electrolyzers. We standardize the assembly by binding the ionic resin into an ionomer wafer and utilize Computational Fluid Dynamics (CFD) to design gaskets for uniform fluid flow. Here, we employ the distribution of relaxation times (DRT) method to determine that anionic-conducting interfaces are the primary contributor to energy losses. To address this, we demonstrate that enhancing the contact between the cathode and the anion exchange membrane (AEM) and the AEM-ionic resin interface allows for low overpotential in deionized water operation.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 2549272

Report Number(s):: NREL/JA--5900-91640

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 3 Vol. 10; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (69)

Gas–liquid–solid reaction system for CO₂ electroreduction to formate without using supporting electrolyte Díaz‐Sainz, Guillermo; Alvarez‐Guerra, Manuel; Solla‐Gullón, José AIChE Journal, Vol. 66, Issue 9 https://doi.org/10.1002/aic.16299	journal	July 2020
Insights into hydrophobicity‐tuned catalyst microenvironment in gas diffusion electrode for boosting CO₂ electrolysis Dong, Lei; Yu, Tingting; Sheng, Xuedi AIChE Journal, Vol. 70, Issue 6 https://doi.org/10.1002/aic.18408	journal	March 2024
Catholyte-Free Electrocatalytic CO ₂ Reduction to Formate Lee, Wonhee; Kim, Young Eun; Youn, Min Hye Angewandte Chemie International Edition, Vol. 57, Issue 23 https://doi.org/10.1002/anie.201803501	journal	May 2018
Sulphonated cross‐linked polystyrene: A monofunctional cation‐exchange resin Pepper, K. W. Journal of Applied Chemistry, Vol. 1, Issue 3 https://doi.org/10.1002/jctb.5010010307	journal	March 1951
Electrochemical CO₂ Reduction on Metal Electrodes Hori, Y.; Vayenas, Constantinos G.; White, Ralph E. Modern Aspects of Electrochemistry, p. 89-189 https://doi.org/10.1007/978-0-387-49489-0_3	book	January 2008
The effect of the gas void distribution on the ohmic resistance during water electrolytes Bongenaar-Schlenter, B. E.; Janssen, L. J. J.; Van Stralen, S. J. D. Journal of Applied Electrochemistry, Vol. 15, Issue 4 https://doi.org/10.1007/BF01059295	journal	July 1985
Enhancing PEM water electrolysis efficiency by reducing the extent of Ti gas diffusion layer passivation Bystron, T.; Vesely, M.; Paidar, M. Journal of Applied Electrochemistry, Vol. 48, Issue 6 https://doi.org/10.1007/s10800-018-1174-6	journal	March 2018
Catalyst coated membrane electrodes for the gas phase CO2 electroreduction to formate Díaz-Sainz, Guillermo; Alvarez-Guerra, Manuel; Solla-Gullón, José Catalysis Today, Vol. 346 https://doi.org/10.1016/j.cattod.2018.11.073	journal	April 2020
A focus on the electrolyte: Realizing CO2 electroreduction from aqueous solution to pure water Zhao, Jia Yue; Liu, Yuanwei; Li, Wenjing Chem Catalysis, Vol. 3, Issue 1 https://doi.org/10.1016/j.checat.2022.11.010	journal	January 2023
How the distribution of relaxation times enhances complex equivalent circuit models for fuel cells Dierickx, Sebastian; Weber, André; Ivers-Tiffée, Ellen Electrochimica Acta, Vol. 355 https://doi.org/10.1016/j.electacta.2020.136764	journal	September 2020
Optimization of catalyst-coated membranes for enhancing performance in proton exchange membrane electrolyzer cells Xie, Zhiqiang; Yu, Shule; Yang, Gaoqiang International Journal of Hydrogen Energy, Vol. 46, Issue 1 https://doi.org/10.1016/j.ijhydene.2020.09.239	journal	January 2021
Techno-economic assessment of CO2 direct air capture plants Fasihi, Mahdi; Efimova, Olga; Breyer, Christian Journal of Cleaner Production, Vol. 224 https://doi.org/10.1016/j.jclepro.2019.03.086	journal	July 2019
Electrochemical conversion of CO2 to formic acid utilizing Sustainion™ membranes Yang, Hongzhou; Kaczur, Jerry J.; Sajjad, Syed Dawar Journal of CO2 Utilization, Vol. 20 https://doi.org/10.1016/j.jcou.2017.04.011	journal	July 2017
Performance and long-term stability of CO2 conversion to formic acid using a three-compartment electrolyzer design Yang, Hongzhou; Kaczur, Jerry J.; Sajjad, Syed Dawar Journal of CO2 Utilization, Vol. 42 https://doi.org/10.1016/j.jcou.2020.101349	journal	December 2020
A microchanneled solid electrolyte for carbon-efficient CO2 electrolysis Xu, Yi; Miao, Rui Kai; Edwards, Jonathan P. Joule, Vol. 6, Issue 6 https://doi.org/10.1016/j.joule.2022.04.023	journal	June 2022
Kinetics and mechanism of heterogeneous voltage-driven water-dissociation catalysis Chen, Lihaokun; Xu, Qiucheng; Boettcher, Shannon W. Joule, Vol. 7, Issue 8 https://doi.org/10.1016/j.joule.2023.06.011	journal	August 2023
Advancing electrochemical impedance analysis through innovations in the distribution of relaxation times method Maradesa, Adeleke; Py, Baptiste; Huang, Jake Joule, Vol. 8, Issue 7 https://doi.org/10.1016/j.joule.2024.05.008	journal	July 2024
Advanced impedance study of polymer electrolyte membrane single cells by means of distribution of relaxation times Heinzmann, Marcel; Weber, André; Ivers-Tiffée, Ellen Journal of Power Sources, Vol. 402 https://doi.org/10.1016/j.jpowsour.2018.09.004	journal	October 2018
A review on the distribution of relaxation times analysis: A powerful tool for process identification of electrochemical systems Plank, Christian; Rüther, Tom; Jahn, Leonard Journal of Power Sources, Vol. 594 https://doi.org/10.1016/j.jpowsour.2023.233845	journal	February 2024
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
Describing ion transport and water splitting in an electrodialysis stack with bipolar membranes by a 2-D model: Experimental validation León, T.; López, J.; Torres, R. Journal of Membrane Science, Vol. 660 https://doi.org/10.1016/j.memsci.2022.120835	journal	October 2022
Anion exchange membranes: The effect of reinforcement in water and electrolyte Luo, Xiaoyan; Kushner, Douglas I.; Kusoglu, Ahmet Journal of Membrane Science, Vol. 685 https://doi.org/10.1016/j.memsci.2023.121945	journal	November 2023
Techno-economic assessment of emerging CO2 electrolysis technologies Barecka, Magda H.; Ager, Joel W.; Lapkin, Alexei A. STAR Protocols, Vol. 2, Issue 4 https://doi.org/10.1016/j.xpro.2021.100889	journal	December 2021
Electrolytic CO ₂ Reduction in a Flow Cell Weekes, David M.; Salvatore, Danielle A.; Reyes, Angelica Accounts of Chemical Research, Vol. 51, Issue 4 https://doi.org/10.1021/acs.accounts.8b00010	journal	March 2018
Impact of the PiperION Anion Exchange Membrane Thickness on the Performance of a CO₂-to-HCOOH Three-Compartment Electrolyzer Rutjens, Bastian; von Foerster, Konstantin; Schmid, Bernhard Industrial & Engineering Chemistry Research, Vol. 63, Issue 9 https://doi.org/10.1021/acs.iecr.3c04459	journal	February 2024
High-Pressure Electrochemical Reduction of CO ₂ to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics Ramdin, Mahinder; Morrison, Andrew R. T.; de Groen, Mariette Industrial & Engineering Chemistry Research, Vol. 58, Issue 51 https://doi.org/10.1021/acs.iecr.9b03970	journal	November 2019
Pure-Water-Fed Forward-Bias Bipolar Membrane CO₂ Electrolyzer Heßelmann, Matthias; Lee, Jason Keonhag; Chae, Sudong ACS Applied Materials & Interfaces, Vol. 16, Issue 19 https://doi.org/10.1021/acsami.4c02799	journal	May 2024
How Temperature Affects the Selectivity of the Electrochemical CO₂ Reduction on Copper Vos, Rafaël E.; Kolmeijer, Kees E.; Jacobs, Thimo S. ACS Catalysis, Vol. 13, Issue 12 https://doi.org/10.1021/acscatal.3c00706	journal	June 2023
Recent Advances in Solar-Driven Carbon Dioxide Conversion: Expectations versus Reality He, Jie; Janáky, Csaba ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00645	journal	May 2020
CO ₂ Electroreduction to Formate at a Partial Current Density of 930 mA cm ^–2 with InP Colloidal Quantum Dot Derived Catalysts Grigioni, Ivan; Sagar, Laxmi Kishore; Li, Yuguang C. ACS Energy Letters, Vol. 6, Issue 1 https://doi.org/10.1021/acsenergylett.0c02165	journal	December 2020
Self-Cleaning CO ₂ Reduction Systems: Unsteady Electrochemical Forcing Enables Stability Xu, Yi; Edwards, Jonathan P.; Liu, Shijie ACS Energy Letters, Vol. 6, Issue 2 https://doi.org/10.1021/acsenergylett.0c02401	journal	February 2021
Ethylene Electrosynthesis: A Comparative Techno-economic Analysis of Alkaline vs Membrane Electrode Assembly vs CO ₂ –CO–C ₂ H ₄ Tandems Sisler, Jared; Khan, Shaihroz; Ip, Alexander H. ACS Energy Letters, Vol. 6, Issue 3 https://doi.org/10.1021/acsenergylett.0c02633	journal	February 2021
Downstream of the CO ₂ Electrolyzer: Assessing the Energy Intensity of Product Separation Alerte, Théo; Edwards, Jonathan P.; Gabardo, Christine M. ACS Energy Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acsenergylett.1c02263	journal	November 2021
Zero-Gap Electrochemical CO₂ Reduction Cells: Challenges and Operational Strategies for Prevention of Salt Precipitation Sassenburg, Mark; Kelly, Maria; Subramanian, Siddhartha ACS Energy Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsenergylett.2c01885	journal	December 2022
Voltage Loss Diagnosis in CO₂ Electrolyzers Using Five-Electrode Technique Hansen, Kentaro U.; Cherniack, Luke H.; Jiao, Feng ACS Energy Letters, Vol. 7, Issue 12 https://doi.org/10.1021/acsenergylett.2c02096	journal	November 2022
Operando Diagnosis of MEA-Type CO₂ Electrolyzer via Distribution of Relaxation Times Analysis Qu, Yunhao; Yang, Kaicong; Li, Wenzheng ACS Energy Letters, Vol. 9, Issue 6 https://doi.org/10.1021/acsenergylett.4c00951	journal	May 2024
Techno-Economic Analysis of Postcombustion Processes for the Capture of Carbon Dioxide from Power Plant Flue Gas Schach, Marc-Oliver; Schneider, Rüdiger; Schramm, Henning Industrial & Engineering Chemistry Research, Vol. 49, Issue 5 https://doi.org/10.1021/ie900514t	journal	February 2010
Electrochemical CO2 reduction to high-concentration pure formic acid solutions in an all-solid-state reactor Fan, Lei; Xia, Chuan; Zhu, Peng Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17403-1	journal	July 2020
Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment Xing, Zhuo; Hu, Lin; Ripatti, Donald S. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-020-20397-5	journal	January 2021
Stable, active CO2 reduction to formate via redox-modulated stabilization of active sites Li, Le; Ozden, Adnan; Guo, Shuyi Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25573-9	journal	September 2021
Stabilizing indium sulfide for CO2 electroreduction to formate at high rate by zinc incorporation Chi, Li-Ping; Niu, Zhuang-Zhuang; Zhang, Xiao-Long Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26124-y	journal	October 2021
Coverage enhancement accelerates acidic CO2 electrolysis at ampere-level current with high energy and carbon efficiencies Yu, Xiaohan; Xu, Yuting; Li, Le Nature Communications, Vol. 15, Issue 1 https://doi.org/10.1038/s41467-024-45988-4	journal	February 2024
Advancing electrodeionization with conductive ionomer binders that immobilize ion-exchange resin particles into porous wafer substrates Palakkal, Varada Menon; Valentino, Lauren; Lei, Qi npj Clean Water, Vol. 3, Issue 1 https://doi.org/10.1038/s41545-020-0052-z	journal	January 2020
Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer Chen, Mohan; Zheng, Lixin; Santra, Biswajit Nature Chemistry, Vol. 10, Issue 4 https://doi.org/10.1038/s41557-018-0010-2	journal	March 2018
Continuous production of pure liquid fuel solutions via electrocatalytic CO2 reduction using solid-electrolyte devices Xia, Chuan; Zhu, Peng; Jiang, Qiu Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0451-x	journal	September 2019
Operando cathode activation with alkali metal cations for high current density operation of water-fed zero-gap carbon dioxide electrolysers Endrődi, B.; Samu, A.; Kecsenovity, E. Nature Energy, Vol. 6, Issue 4 https://doi.org/10.1038/s41560-021-00813-w	journal	April 2021
Bifunctional ionomers for efficient co-electrolysis of CO2 and pure water towards ethylene production at industrial-scale current densities Li, Wenzheng; Yin, Zhenglei; Gao, Zeyu Nature Energy, Vol. 7, Issue 9 https://doi.org/10.1038/s41560-022-01092-9	journal	August 2022
Energy- and carbon-efficient CO2/CO electrolysis to multicarbon products via asymmetric ion migration–adsorption Ozden, Adnan; Li, Jun; Kandambeth, Sharath Nature Energy, Vol. 8, Issue 2 https://doi.org/10.1038/s41560-022-01188-2	journal	January 2023
Pure-water-fed, electrocatalytic CO2 reduction to ethylene beyond 1,000 h stability at 10 A She, Xiaojie; Zhai, Lingling; Wang, Yifei Nature Energy, Vol. 9, Issue 1 https://doi.org/10.1038/s41560-023-01415-4	journal	January 2024
An industrial perspective on catalysts for low-temperature CO2 electrolysis Masel, Richard I.; Liu, Zengcai; Yang, Hongzhou Nature Nanotechnology, Vol. 16, Issue 2 https://doi.org/10.1038/s41565-020-00823-x	journal	January 2021
High current density electroreduction of CO2 into formate with tin oxide nanospheres Nguyen-Phan, Thuy-Duong; Hu, Leiming; Howard, Bret H. Scientific Reports, Vol. 12, Issue 1 https://doi.org/10.1038/s41598-022-11890-6	journal	May 2022
Techno-economic assessment of low-temperature carbon dioxide electrolysis Shin, Haeun; Hansen, Kentaro U.; Jiao, Feng Nature Sustainability https://doi.org/10.1038/s41893-021-00739-x	journal	July 2021
Enhancing acetate selectivity by coupling anodic oxidation to carbon monoxide electroreduction Overa, Sean; Crandall, Bradie S.; Shrimant, Bharat Nature Catalysis, Vol. 5, Issue 8 https://doi.org/10.1038/s41929-022-00828-w	journal	August 2022
An alkaline polymer electrolyte CO ₂ electrolyzer operated with pure water Yin, Zhenglei; Peng, Hanqing; Wei, Xing Energy & Environmental Science, Vol. 12, Issue 8 https://doi.org/10.1039/C9EE01204D	journal	January 2019
Promoting water-splitting in Janus bipolar ion-exchange resin wafers for electrodeionization Jordan, Matthew L.; Valentino, Lauren; Nazyrynbekova, Nargiza Molecular Systems Design & Engineering, Vol. 5, Issue 5 https://doi.org/10.1039/C9ME00179D	journal	January 2020
Strategies for the mitigation of salt precipitation in zero-gap CO₂ electrolyzers producing CO Disch, Joey; Bohn, Luca; Metzler, Lukas Journal of Materials Chemistry A, Vol. 11, Issue 14 https://doi.org/10.1039/D2TA09966G	journal	January 2023
Single atom catalysts for water electrolysis: from catalyst-coated substrate to catalyst-coated membrane Lee, Sol A.; Jun, Sang Eon; Park, Sun Hwa EES Catalysis, Vol. 2, Issue 1 https://doi.org/10.1039/D3EY00165B	journal	January 2024
Insights into zero-gap CO₂ electrolysis at elevated temperatures Giron Rodriguez, Carlos A.; Kani, Nishithan C.; Moss, Asger B. EES Catalysis, Vol. 2, Issue 3 https://doi.org/10.1039/D3EY00224A	journal	January 2024
Recent advancements in catalyst coated membranes for water electrolysis: a critical review Vinodh, Rajangam; Palanivel, Tamilazhagan; Kalanur, Shankara Sharanappa Energy Advances, Vol. 3, Issue 6 https://doi.org/10.1039/D4YA00143E	journal	January 2024
Ion Exchange and the Swelling of Ion-exchange Resins Samsonov, G. V.; Pasechnik, V. A. Russian Chemical Reviews, Vol. 38, Issue 7 https://doi.org/10.1070/RC1969v038n07ABEH001761	journal	July 1969
Economic and energetic analysis of capturing CO2 from ambient air House, K. Z.; Baclig, A. C.; Ranjan, M. Proceedings of the National Academy of Sciences, Vol. 108, Issue 51 https://doi.org/10.1073/pnas.1012253108	journal	December 2011
CO ₂ electrolysis to multicarbon products at activities greater than 1 A cm ⁻² García de Arquer, F. Pelayo; Dinh, Cao-Thang; Ozden, Adnan Science, Vol. 367, Issue 6478 https://doi.org/10.1126/science.aay4217	journal	February 2020
Passivity and Corrosion Resistance of Titanium and Its Alloys Tomashov, N. D.; Altovsky, R. M.; Chernova, G. P. Journal of The Electrochemical Society, Vol. 108, Issue 2 https://doi.org/10.1149/1.2428023	journal	January 1961
An Improved Catalyst-Coated Membrane Structure for PEM Water Electrolyzer Song, Shidong; Zhang, Huamin; Liu, Bo Electrochemical and Solid-State Letters, Vol. 10, Issue 8 https://doi.org/10.1149/1.2743823	journal	January 2007
KOH vs Deionized Water Operation in Anion Exchange Membrane Electrolyzers Hassan, Noor Ul; Zheng, Yiwei; Kohl, Paul A. Journal of The Electrochemical Society, Vol. 169, Issue 4 https://doi.org/10.1149/1945-7111/ac5f1d	journal	April 2022
Anolyte Enhances Catalyst Utilization and Ion Transport Inside a CO₂ Electrolyzer Cathode Saha, Prantik; Henckel, Danielle; Baez-Cotto, Carlos Journal of The Electrochemical Society, Vol. 170, Issue 1 https://doi.org/10.1149/1945-7111/acb01d	journal	January 2023
Effect of Cations on the Electrochemical Conversion of CO₂ to CO Thorson, M. R.; Siil, K. I.; Kenis, P. J. A. Journal of the Electrochemical Society, Vol. 160, Issue 1, p. F69-F74 https://doi.org/10.1149/2.052301jes	journal	November 2012
Efficient Electrochemical Flow System with Improved Anode for the Conversion of CO₂ to CO Ma, S.; Luo, R.; Moniri, S. Journal of the Electrochemical Society, Vol. 161, Issue 10, p. F1124-F1131 https://doi.org/10.1149/2.1201410jes	journal	January 2014
Demonstration of a three compartment solar electrolyser with gas phase cathode producing formic acid from CO2 and water using Earth abundant metals Thijs, Barbara; Hanssens, Lucas; Heremans, Gino Frontiers in Chemical Engineering, Vol. 4 https://doi.org/10.3389/fceng.2022.1028811	journal	November 2022

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09 BIOMASS FUELS
BIOMASS FUELS
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Interfaces
Layered materials
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Selectivity
distribution of relaxation times
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porous solid electrolyte
scalable

Title: An Interfacial Engineering Approach toward Operation of a Porous Solid Electrolyte CO2 Electrolyzer

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Title: An Interfacial Engineering Approach toward Operation of a Porous Solid Electrolyte CO₂ Electrolyzer