Component Research for Redox Flow Batteries and Open
Component Research for Redox Flow Batteries and Open Batteries Tom Zawodzinski ORNL ORNL is managed by UT-Battelle, LLC for the US Department of Energy Project Overview Overarching Objective: improving energy density without lower power density, driven by work on components We are after GENERAL approaches that cut across battery types, chemistry, operating modes etc Two main elements to our work 1. Test Beds for components 2. New materials for specific battery types based on understanding from test beds. 2 Components Provide Focal Point Components Provide an Organizing Principle Cost Performance
Reliability Supporting component research 3 Electrodes, Membranes, Hardware, Processes Goal: These will help ALL flow battery types Project Challenges: test bed to component solution Challenge Opportunity 1. Dendrites during metal plating, oxide formation on surface 1. Developed new architecture based on understanding key processes 2. Obtaining high performance in RFBs
2. Advanced electrodes, membranes 3. Capacity fade in RFBs 3. Capacity fade in RFBs a. Experimental methods to determine a. Developed and extended methodology cross-over b. Identified several other pathways, b. Other capacity fade mechanisms? 4 designing methods to test, control 4. Cost, performance of non-aqueous
system 4. Developed low cost membrane additives, testing new couples 5. Relevant test hardware 5. Designed stacks for replaceable parts; designed several new durability test approaches, apparatuses; need resources to implement. Information from Test beds (Test beds developed over Years) Need to Know Need to Know Conductivity, cross-over, other transport for different membrane, electrolyte chemistry
Electrodes Test beds Test beds Rigorous transport theory, experiments that match Conductivity Cross-over cellsmulti-detection Material stability Results Electrode processes, kinetics,
mass transport Wettability, accessible surface Defined test methods reflect operating conditions Approaches to new materials Collaborations: SNL, vendors Membrane Cells, electrochemical methods Critical performance parameters vs. structure, composition Design new tests: capacity fade, durability Results High performance Improved architecture No need to develop specific catalysts in some cases (VRBs) Testbed Evolution: New test methods, new approaches, details for different chemistry Results inform next material development, cell tests
5 Components: Adaptable Building Blocks Electrolytes Electrodes Porous Flow Through Membranes for Flow Electrodes Batteries Membrane structure effects on permeation, conductivity probeddrives design SEM image 2.5EA Carbon Felt at 150x Mag Metal Plating Zn Non-aqueous Electrolytes (O Zn 2H) 4
Air Electrodes Asymmetr ic 6 OH- 2e Project Metrics and Milestones: One for each task, bold) Task: Metal-air (Zn-air) Batteries: Zn Electrodes Published descriptions of studies of structured Zn electrodes for high performance, systematically understanding electrode losses during charge and discharge. Task: Metal-air (Zn-air) Batteries Implement a new, custom synthesized solid polymer electrolyte for this battery, comparing conductivity and reagent cross-over parameters to optimize selectivity for several compositions. Task: Conventional Flow Batteries: Components New membrane characterization, partly in collaboration with SNL (Fujimoto) in a submitted publication. Publish Donnan-potential based comparison of multiple membranes and pretreatments. Task : Non-aqueous Flow Batteries: Develop high solubility, medium voltage redox couple for use with high performance electrolytes.
7 Project Results: test bed highlight New measurement methods for cross-over UV-vis detection of ferricyanide New electrochemical method developed for Zn, peroxide AEM after 10 minutes CEM after 5 hours Other results New apparatus designed for accelerated probe of stability of aq. organics Developed analytical framework and methods for probing capacity fade 8 Project Results: component highlight Membranes for non-aqueous RFBs Found cheap membrane modification method to decouple conductivity and cross-over For same voltage drop, decreased cross-over rate by 100-fold relative to conventional cation
Asymmetri c Asymmetric Currently testing in operating NARFB cell Approach could be applicable to all electrolyte types 9 Project Results-Publications etc. Peng, J. and T. A. Zawodzinski (2019). "Describing ion exchange membrane-electrolyte interactions for high electrolyte concentrations used in electrochemical reactors J. Memb. Sci. Wittman, R. M., et al. (2019). "Elucidating mechanisms of oxide growth and surface passivation on zinc thin film electrodes in alkaline solutions using the electrochemical quartz crystal microbalance." J. Power Sources 438: 227034. Sun, C., et al. (2019). "Elucidation of the interplay between vanadium species and charge- discharge processes in VRFBs by Raman spectroscopy." Electrochim. Acta 318: 913-921. Peng, J. and T. A. Zawodzinski (2018). "Ion transport in phase-separated single ion conductors." J. Membr. Sci. 555: 38-44.
Peng, J., et al. (2018). "The ion and water transport properties of K+ and Na+ form perfluorosulfonic acid polymer." Electrochim. Acta 282: 544-554. Peng, J., et al. (2018). "Transport Properties of Perfluorosulfonate Membranes Ion Exchanged with Cations." ACS Appl. Mater. Interfaces 10(44): 38418-38430. Ke, X., et al. (2018). "Rechargeable redox flow batteries: flow fields, stacks and design considerations." Chem. Soc. Rev. 47(23): 8721-8743. 10 Publications in process, September 2019 1. 2. 3. 4. 5. 6. 7. 8. 9. 11 Use of Carbon Supports to Improve Performance of Negative Electrode of Zn air batteries; Reed M. Wittman and Thomas A. Zawodzinski
COMSOL Modeling of Electrochemical performance of microfludic in situ Liquid ec-S/TEM Cell in Quiescent Electrolyte, Reed M. Wittman, Robert L. Sacci, Raymond R. Unocic, Thomas A. Zawodzinski Changes in Alkaline Zinc Passivation Mechanism from Variations in OH - Concentration Reed M. Wittman, Robert L Sacci, Thomas A Zawodzinski Evaluating Cation Transport in Membranes for Nonaqueous Flow Batteries, Kun Lou, Jing Peng, Zhijiang Tang, Thomas A. Zawodzinski Dependence of Membrane Transport Properties on Acetonitrile Content in TXA-exchanged IEMs, Kun Lou, Jing Peng, Zhijiang Tang, Thomas A. Zawodzinski Nanoscale Mobility of Organic Cations in ACN-swollen PFSA Membranes, Kun Lou and TZ, Kun Lou and Thomas A. Zawodzinski IR Studies of Stepwise Solvation of Organic Cations in PFSA Membranes, Kun Lou and Thomas A. Zawodzinski Hydrogen Bonding and the Origin of the Conductivity Peak in Acid-loaded PFSA Membranes, Kun Lou, Vito DiNoto and Thomas A. Zawodzinski The Influence of Complexation Chemistry on Redox Flow Battery Behavior, Laura Meda, Chiara Gambaro, Chuanyu Sun, Agnieszka Zlotorowicz, Keti Vezzu, Enrico Negro, Vito Di Noto, Giuseppe Pace, Thomas A. Zawodzinski Looking Forward Next FY Test Beds Larger scale testing-reactant distribution New testing Focal Point: Capacity fade mechanisms Non-cross-over mechanisms Electrode evolution during test Side-reactions Coupled solution chemistry
Approaches 1. New experiments and other approaches to probe capacity fade 2. Scaled-up cell designs 3. Stack designed to be pullapart(materials replaceable) Combine models, experiments More emphasis on aqueous organics: accelerated test designed Next FY New Components Cell tests of NARFBs New membranes specifically for Zn batteries Membrane chemistry designed based on Donnan derived specs, generalizing discovery from this year 12 Approaches 1. Add membrane additive to electrolyte solution 2. Zn-peroxide battery testing, analysis 3. Analogous additive chemistry
for aqueous systems? Project Contacts Thanks to Imre Gyuk and OE Project Team ORNL: Tom Zawodzinski, Robert Sacci, Reed Wittman, Kun Lou UTK: Gabriel Goenaga, Adam Imel, Nelly Cantillo University of Massachusetts: Pat Cappillino SNL: Cy Fujimoto and co. Industry: Electrosynthesis Co.* Point of Contact: Tom Zawodzinski [email protected] 13 Project Contacts Thanks to Imre Gyuk and OE Questions? Point of Contact: Tom Zawodzinski [email protected] 14
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