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Inorganic ion exchange membrane fuel cell quarterly report, period ending 10 oct. 1964
Zirconium dioxide, phosphoric acid membranes for hydrogen oxygen fuel cell
Fuel cell ion-exchange membrane investigation
The present deficiencies in the fluorocarbon sulfonic acid membrane used as the solid polymer electrolyte in the H2/O2 fuel cell are studied. Considered are: Adhesives selection, elastomeric formulations, scavenger exploration, and membrane characterization. The significant data are interpreted and recommendations are given for both short and long range further investigations in two of the four major areas: membrane adhesives and membrane stabilization.
Improved ion exchange membrane
Membrane, made from commercially-available hollow fibers, is used in reverse osmosis, or dialysis. Fiber has skin layers which pass only small molecules. Macromolecules cannot penetrate skin. Fibers can also be used to remove other undesirable anions, such as phosphate, sulfate, carbonate, and uranium in form of uranium-sulfate complex.
Game Changing Development Program - Next Generation Life Support Project: Oxygen Recovery From Carbon Dioxide Using Ion Exchange Membrane Electrolysis Technology
This report summarizes the Phase I research and development work performed during the March 13, 2015 to July 13, 2016 period. The proposal for this work was submitted in response to NASA Research Announcement NNH14ZOA001N, "Space Technology Research, Development, Demonstration, and Infusion 2014 (SpaceTech-REDDI-2014)," Appendix 14GCD-C2 "Game Changing Development Program, Advanced Oxygen Recovery for Spacecraft Life Support Systems Appendix" The Task Agreement for this Phase I work is Document Control Number: GCDP-02-TA-15015. The objective of the Phase I project was to demonstrate in laboratories two Engineering Development Units (EDU) that perform critical functions of the low temperature carbon dioxide electrolysis and the catalytic conversion of carbon monoxide into carbon and carbon dioxide. The low temperature carbon dioxide electrolysis EDU was built by the University of Delaware with Dr. Feng Jiao as the principal investigator in charge of this EDU development (under NASA Contract NNC15CA04C). The carbon monoxide catalytic conversion EDU was built by the NASA Glenn Research Center with Kenneth Burke as the principal investigator and overall project leader for the development of both EDUs. Both EDUs were successfully developed and demonstrated the critical functions for each process. The carbon dioxide electrolysis EDU was delivered to the NASA Johnson Space Center and the carbon monoxide catalytic conversion EDU was delivered to the NASA Marshall Spaceflight Center.
Standard Operating Protocol for Ion-Exchange Capacity of Anion Exchange Membranes
Ion-exchange capacity (IEC) is the measure of a material’s capability to displace ions formerly incorporated within its structure. IEC is a key feature of anion-exchange membranes (AEM), as it determines the AEM’s ability to conduct the ions required to sustain the electrochemical reactions where they are utilized. As an intrinsic property, measuring the IEC accurately is essential to study AEMs and understand their performance within devices. In this method article, a facile and accurate standard operating procedure (SOP) to measure the IEC of AEMs is proposed. When compared to conventional acid-base back-titration or Mohr titration, the proposed method combines the fast reaction between silver and halide ions and the accuracy of the potentiometric titration, providing a convenient and precise protocol for researchers in the field.
Phosphate anion-quaternary ammonium ion pair coordinated polymer membranes
Ion exchange membranes materials according to the present disclosure exhibit improved conductivity at low and intermediate relative humidity without sacrificing mechanical strength. Polymers are provided that include a backbone with one or more aryl groups, a halocarbyl group, and a halocarbyl side chain attached to the backbone, wherein the halocarbyl side chain includes a halide separated from the backbone by a hydrocarbyl chain, a hydrocarbyl ring, or combinations thereof. The halide is substituted with a tertiary amine and halide anions are then exchanged with hydroxide anions. The polymers are then contacted with phosphoric acid, which is deprotonated by the hydroxide ions, forming anions which enhance interactions with adjacent quaternary ammonium groups and induce excess phosphoric acid molecules to cluster around those quaternary ammonium groups. The membranes exhibit negligible dopant leaching even at high relative humidity.
Understanding and Manipulating Counterion Condensation within Charged Polymer Electrolytes for Selective and Low Resistant Membrane Separations
Polymeric ion-exchange membranes are found at the heart of numerous electrochemical systems spanning separations (electrodialysis and membrane capacitive deionization) and energy conversion and storage (flow batteries, fuel cells, and electrolyzers). The ion-exchange membrane separators need to be ion conducting but electron insulating, and in many scenarios selective for a particular ion to conduct. Because of their polymeric nature, the molecular architectures of ion-exchange membranes lack the molecular precision found in many inorganic materials. Plus, they contain numerous structural defects that impede ionic transport. As a result of their poor structure, it has been difficult to carefully probe the underlying physics that governs ion transport in ion-exchange membranes. We investigated counterion condensation phenomena in ion-exchange membranes and correlated it to bulk ionic charge transport and selectivity in precisely defined and long-range ordered materials afforded through the principles of directed self-assembly. A multi-faceted approach spanning i.) advanced metrology, two-dimensional atomic force microscopy, x-ray scattering, and ion-exchange equilibria, and ii.) molecular simulations (classical molecular dynamics and ab-inito molecular dynamics) that bridge multiple time and length scales, were employed to correlate the extent of counterion condensation to ionic conductivity and selectivity. After uncovering the extent of the condensation phenomena in this project, new macromolecular chemistries were employed to manipulate the ion pairing interactions of the condensed counterions to tethered ions on the polymer backbone so more facile and selective conduction rates can be attained. The research has aided in the rational design of polymeric ion-exchange membrane separators with high current density for electrochemical systems and subsequently better energy efficiency.
Fabrication of a composite anion exchange membrane with aligned ion channels for a high-performance non-aqueous vanadium redox flow battery
Fabrication of high-conductivity ion exchange membranes (IEMs) is crucial to improve the performance of non-aqueous vanadium redox flow batteries (NAVRFBs). In the present work, anion exchange membranes with high-conductivity were fabricated by aligning ion channels of the polymer electrolyte impregnated in porous polytetrafluoroethylene (PTFE) under electric fields. It was observed that the ion channels of the polymer electrolyte were uniformly orientated in the atomic-force microscopy image. Its morphological change could minimize detouring of the transport of BF 4 - ions. The results showed through-plane conductivity was improved from 12.7 to 33.1 mS cm -1 . The dimensional properties of the fabricated membranes were also enhanced compared with its cast membrane owing to the reinforcing effect of the substrate. Especially, the NAVRFB assembled with the optimized membrane showed increased capacities, with a 97% coulombic efficiency and 70% energy efficiency at 80 mA cm -2 . Furthermore, the optimized membrane made it possible to operate the NAVRFB at 120 mA cm -2 . Its operating current density was 120 times higher than that of a frequently used AHA membrane for RFBs.
Electrostatic limits on charge selectivity in ultrahigh charge density polymer membranes
Ion-exchange membranes (IEMs) with ultrahigh charge densities offer the promise of enhanced ion transport for electrochemical technologies, yet the fundamental limits of this membrane design strategy are not yet understood. In this work, we present a systematic study of bis(1-vinyl-3-imidazolium) cross-linked polymer membranes with fixed charge contents ranging from 6 to 9 mol/L[dry polymer], synthesized to isolate the effects of charge density at constant membrane water content. While ionic conductivity increases monotonically with increasing charge density, a sharp decline in charge selectivity is observed for the most densely charged membranes, defying conventional expectations. Structural, thermal, and mechanical analyses reveal a critical onset of network disruption and anomalous ion partitioning behavior in these densely charged membranes. With proper consideration of cross-linker geometry, these results are interpreted using Manning's counter-ion condensation theory, which suggests that closely packed charged cross-linkers amplify inter-chain electrostatic interactions and trigger excess counter-ion condensation. Our findings suggest that, beyond a threshold spacing between fixed charges, increased functionalization may harm rather than help charge selectivity of IEMs.
Membrane consisting of polyquaternary amine ion exchange polymer network interpenetrating the chains of thermoplastic matrix polymer
An ion exchange membrane was formed from a solution containing dissolved matrix polymer and a set of monomers which are capable of reacting to form a polyquaternary ion exchange material; for example vinyl pyride and a dihalo hydrocarbon. After casting solution and evaporation of the volatile component's, a relatively strong ion exchange membrane was obtained which is capable of removing anions, such as nitrate or chromate from water. The ion exchange polymer forms an interpenetrating network with the chains of the matrix polymer.
Method of making membranes
Inorganic ion exchange membrane electrolytes for fuel cell use
Wastewater Brine Purification and Recovery through Electrodialysis Ion Exchange
Reutilizing resources onboard the International Space Station (ISS) and for future deep space missions are critical for mission longevity and sustainability. Wastewater brine produced from water recovery systems contain chemical species that could be processed into a potential fertilizer for future plant systems. This can be achieved through a process called electrodialysis ion exchange. Wastewater containing inorganic salt components are fed through a series of ion exchange membranes to produce fertilizer (a phosphate rich stream), electrolysis-grade water, and other useful commodities. Electrodialysis cells consisting of anion and cation exchange membranes, monovalent anion exchange membranes, and bipolar membranes were utilized to achieve selective ion exchange. The use of the electrodialysis cells were effective for both water extraction and ion separation. Ions successfully diffused across their respective membranes into the concentrate, acid, and base streams. This resulted in pure water, a phosphate rich stream, and a separate anion/hydrogen and cation/hydroxide stream. However, sulfate and some phosphate ions were able to diffuse through the monovalent anion exchange membrane into the acid stream. This resulted in predominantly phosphate ions remaining in the concentrate. Optimization of the process was accomplished by altering flowrates of each stream and initial volumes, adjusting the power input and resulting current through each cell, and varying the starting parameters by splitting the inorganic waste input into the diluate and the concentrate. As expected, increasing the flowrate and the power input to each cell reduced the overall time of the process. However, mission constraints may require a longer duration process in order to reduce the power consumption. Further analysis will be required to determine the power input necessary to achieve ion diffusion effectively and in a timely manner.
A high-performance hydroxide exchange membrane enabled by Cu 2+ -crosslinked chitosan
We report ion exchange membranes are widely used to selectively transport ions in various electrochemical devices. Hydroxide exchange membranes (HEMs) are promising to couple with lower cost platinum-free electrocatalysts used in alkaline conditions, but are not stable enough in strong alkaline solutions. Herein, we present a Cu 2+ -crosslinked chitosan (chitosan-Cu) material as a stable and high-performance HEM. The Cu 2+ ions are coordinated with the amino and hydroxyl groups of chitosan to crosslink the chitosan chains, forming hexagonal nanochannels (similar to 1nm in diameter) that can accommodate water diffusion and facilitate fast ion transport, with a high hydroxide conductivity of 67 ms cm -1 at room temperature. The Cu 2+ coordination also enhances the mechanical strength of the membrane, reduces its permeability and, most importantly, improves its stability in alkaline solution (only 5% conductivity loss at 80 degrees C after 1,000 h). These advantages make chitosan-Cu an outstanding HEM, which we demonstrate in a direct methanol fuel cell that exhibits a high power density of 305 mWcm -2 . The design principle of the chitosan-Cu HEM, in which ion transport channels are generated in the polymer through metal-crosslinking of polar functional groups, could inspire the synthesis of many ion exchange membranes for ion transport, ion sieving, ion filtration and more.
Single and Dual-Solute Transport in Quaternary Ammonium-Functionalized Anion Exchange Membranes: Isolating the Impact of Water Volume Fraction
Membranes are essential components of photoelectrochemical CO 2 reduction cells (PEC-CRC), as they regulate solute transport and impact device efficiency. These cells are a promising approach for converting carbon dioxide into valuable chemicals. However, electrochemical reactions involve not just a single electrolyte; membrane transport typically includes multiple electrolytes. When a mixture of solutes is present, the presence of one solute in the membrane can impact the diffusion and sorption of other solutes. In complex systems where multiple solutes are diffusing simultaneously through a hydrated, dense polymer membrane, the resulting transport behavior is poorly understood. This study highlights the individual and two solute transport behavior of potassium formate, acetate, and bicarbonate ions in neutral membranes and quaternary ammonium-functionalized anion exchange membranes (AEMs) based on phenyl acrylate polymer backbones. By isolating the effect of water content, we emphasize how fixed charge density and solute-membrane interactions influence transport behavior. In neutral membranes, the diffusivity follows the order of potassium formate > potassium acetate > potassium bicarbonate. However, in AEMs, the order shifts due to changes in ion-membrane interactions, with potassium bicarbonate diffusivity surpassing that of potassium acetate. These results underscore the importance of ion exchange membranes and ion-membrane interaction in modulating transport properties, providing valuable insights for optimizing membranes in electrochemical applications.
Ion-Exchange Membrane-Centric Durability Testing and Degradation Characterization for Industry-Relevant CO 2 Reduction
Electrochemical CO 2 reduction is a promising conversion process for producing value-added fuels and chemicals from electricity and CO 2 as a sustainable carbon feedstock to domestically produce fuels and chemicals from industrial waste. Having reached industrially viable performance metrics with small-scale CO 2 electrolysis cells, the field must now increasingly focus on extending the device durability of large stacks to achieve equivalent metrics for 35,000+ hours to decrease maintenance and capital costs. Reported device lifetimes have increased in recent years, with the longest stability studies for CO, ethylene, and formic acid production being published in 2024–2025 with operation times of 4500, 1000, and 5200 h, respectively. Unfortunately, significant extension of the device durability is still required. Here, we provide an overview of ion-exchange membranes (IEMs) and provide insight into the variety of degradation mechanisms that must be overcome to enable the community to meet durability targets. In an effort to accelerate the extension of device lifetimes, we propose a general approach for characterizing CO 2 electrolysis cell degradation before and after durability testing to better elucidate the mechanisms and failure modes of IEMs in zero-gap cells. Furthermore, we encourage the adoption of operando characterizations in tandem with accelerated stress and durability tests, postulating that their combined applications will be increasingly valuable. We hope that this perspective motivates future durability studies to evaluate degradation across the entire electrolysis cell.
Water production for coffee brewing by electrodeionization
A resin-wafer electrodeionization (RW-EDI) apparatus for purifying water for coffee brewing comprises a cathode; an anode; and multiple porous solid resin wafer exchange units arranged in a stack between the cathode and the anode, and an air distributor adapted and arranged to aerate the water to be purified. Each unit comprises a monovalent cation exchange membrane (CEM), an anion exchange membrane (AEM), and an ion exchange resin wafer between the CEM and the AEM, which is in contact with, and in fluid flow connection with the CEM and AEM. Each resin wafer comprises a cation exchange resin and an anion exchange resin. The units are oriented with the CEM facing the cathode and the AEM facing the anode, with space between the units defining ion concentrate chambers. Bipolar ion exchange membranes separate the anode and cathode from their nearest resin wafer exchange units.
Dilute Regeneration-Driven Membrane Capacitive Deionization of Synthetic Seawater Using Nanopatterned Membranes and Prussian Blue Analog Electrodes
Membrane capacitive deionization (MCDI) offers energy-efficient seawater desalination but is limited at high salinity by membrane resistance and incomplete electrode regeneration. Nanopatterned ion-exchange membranes, dilute regeneration protocols, and Prussian blue analog (PBA)-functionalized electrodes are combined in a flow-by-MCDI cell. Nanopatterned ion-exchange membranes (hexagonal, octagonal, double-ring, rectangular) enhance interfacial ion transport, with hexagonal geometry delivering ≈12.5% greater surface area and the best performance. PBA-functionalized electrodes increase salt adsorption and charge-transfer kinetic rates. The integrated system lowers the area-specific resistance by 45 Ω cm2, resulting in a 500 mV reduction in the cell voltage for a current density of 2 mA cm−2 for a 35 000 ppm NaCl feed. This improves the energy-normalized salt adsorption six fold (64–382 mmol J−1). Low salinity (2000 ppm) and mixed-salt regeneration sustains a ≈39% water recovery and stable performance for at least seven cycles. Overall, combining nanopatterned membranes, which promote confinement-enhanced ion mobility, and PBA electrodes, which enhance salt adsorption, improved the energy efficiency of MCDI.