Search NASA⌕ Search

SEARCH · Search NASA

Results for “ion-exchange membranes”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

78 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electrically regenerated ion-exchange technology: Leveraging faradaic reactions and assessing the effect of co-ion sorption

Capacitive deionization (CDI) technologies have the potential to become cost-competitive alternatives to reverse osmosis for the treatment of brackish waters. In this study, we describe our findings on the effect of co-ion sorption and faradaic side reactions on our ion exchange resin functionalized desalination electrodes which passively capture salt and reject it upon charging. This system, which we previously reported on and refer to as electrically regenerated ion exchange (ERI), avoids the use of expensive ion exchange membranes in an effort to save costs. Surprisingly, we find that, compared to a reference CDI system, ERI electrodes capture salt most effectively at low applied voltages (0.5 mg/cm 3 at 0.8 V). Both CDI and ERI systems also seem to suffer from co-ion sorption effects which negatively impact salt adsorption. However, Faradaic side reactions at higher voltages (1 V and 1.2 V) which we track via pH measurements, serve as a detriment to CDI but seem to facilitate the functionality of ERI.

42 ENGINEERING↗
DOE OSTI2025

Effect of Sulfonation Level on the Percolated Morphology and Proton Conductivity of Hydrated Fluorine-Free Copolymers: Experiments and Simulations

Using all-atom molecular dynamics simulations and a variety of experimental methods, we previously reported on a linear polyethylene with pendant phenyl sulfonated groups precisely on every fifth carbon along the backbone. With increasing relative humidity this fluorine-free polymer self-assembled to form nanoscale water channels and exhibited exceptional proton conductivity. Expanding upon those findings, here we explore partially sulfonated random copolymers, referred to as p 5PhSH-Y. Using either acetyl sulfate or sulfuric acid, a wide range of sulfonation levels were prepared ( Y = 34−98%) corresponding to ion-exchange capacities (IEC) of 2.0−4.4 mmol/g. Combining experimental techniques and all-atom molecular dynamics simulations, we study the effect of Y on water uptake, nanoscale morphology, and the proton/water transport properties of p5PhSH- Y . The proton conductivity of p 5PhSH- Y increases with relative humidity and with Y and achieves values in excess of 0.1 S/cm. These high conductivities are attributed to high IEC and welldeveloped nanoscale percolated hydrophilic domains made possible by the flexible backbone. We quantitatively describe the nature of the water channels using the characteristic distance, channel width distribution, the area per sulfonate group at the hydrophilic/ hydrophobic interface, and the fractal dimension. Notably, the channel widths and the areas per sulfonate group are nominally independent of the level of sulfonation, while depending significantly on the level of hydration. The fractal dimension of the water channels correlates strongly with the water diffusion coefficients calculated from the molecular dynamics (MD) simulations. These findings demonstrate that the p 5PhSH- Y hydrocarbon copolymers can be modified to tune properties, particularly proton conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Atomistic characterization of hydration-dependent fuel cell ionomer nanostructure: validation by vibrational spectroscopy

The development of Nafion alternatives for fuel cells and electrolyzers requires a fundamental understanding of hydration-dependent ion-exchange site acid/base chemistry. We present here reactive force field (ReaxFF) molecular dynamics (MD) simulations of Nafion at varying molar water/ion-exchange-site ratios (λ), which we correlate to our experimental and density functional theory-based vibrational spectra. ReaxFF describes the formation and breaking of covalent bonds, enabling simulations of proton exchange between sulfonic acid/sulfonate groups and water/hydronium. Our MD simulations determine the λ-dependent equilibrium proportions of protonated and deprotonated sites. We find that protonated sites persist across all λ from 0 to 20, challenging the widely accepted notion that all sites are ionized above a threshold λ value (e.g., 3 or 4). Our simulations generate hundreds of realistic exchange site environments, the characterization of which are based on 6 Å radii sulfur-centered ‘inner-spheres’. These inner- and outer-sphere regions elucidate an interplay of stereoelectronic factors that influence protonation states, including the number of inner-sphere waters (Λ). Our simulations produce broad λ-dependent distributions of Λ values, representing non-uniform exchange site hydration. Moreover, we demonstrate that these distributions are specific to both protonated and deprotonated sites, with significant overlap between the two distributions for all non-zero λ. These distributions underpin the IR spectra of hydrated membranes, with each exchange site contributing an IR spectrum characteristic of its protonation state and Λ. We expect that these nanostructural characterizations of Nafion exchange sites will contribute to the development of new ionomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

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

Bipolar membranes (BPMs), which have long seen usage in electrodialysis reactors for the generation of acid and base, have recently demonstrated potential to become critical components in electrochemical synthesis devices. 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 junction as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-devices for electrosynthesis applications. Prior work has modeled ion transport in bipolar membranes in neutral salt solutions for electrodialysis. However, no model exists for the BPM under the harsh applied pH gradients that would be present in electrosynthesis, and there is significant need to explore the effects of the internal hydration on the lifetime and performance of BPMs in such environments. Additionally, a mechanistic understanding of water dissociation catalysis will be required to develop interfacial catalysts that enable the high current density operation required for scalable electrosynthesis of fuels. In this talk, we discuss modeling methodologies and physics inherent in BPMs and present our recent model of ion transport and water dissociation catalysis in BPMs across the pH scale. Specifically, we simulate multi-ion transport for a BPM with various electrolyte combinations on each side of the membrane, demonstrating the significance of co- and counter-ion crossover in BPMs operating under harsh pH gradients. We then investigate effects caused by hydration gradients that occur due to internal ion-exchange and examine potential methods for improving performance and mitigating crossover. Finally, we examine the impact of the interfacial water dissociation catalyst and perform sensitivity analysis on the key properties (catalyst point of zero charge and pKa) that dictate catalyst performance. These results provide information that is critical to developing a comprehensive understanding of multi-component phenomena in BPMs and to informing the design and implementation of BPMs in next-generation devices for the numerous electrosynthesis chemistries that benefit from operation under an applied pH gradient.

Bui, Justin C↗
DOE OSTI2021

CO2 Capture Strategies via Mineralization with Industrial Waste Brines

Large coal-fired power plants (>500 MW) account for 30% of global CO2 emissions, and long-term management of this CO2 to is urgently needed mitigate global temperature increases. Sequestration of CO2 within stable mineral carbonates (e.g., CaCO3) represents an attractive emission reduction strategy because it offers a leakage-free alternative to geological storage of CO2 in an environmentally friendly form. We have previously described a mineralization process in which divalent cations are sourced from various waste streams (e.g., produced water and brackish water) and alkalinity is induced via regenerable ion-exchange materials (Bustillos et. al. Frontiers in Energy Research. 2020, 8, 352). In our process, aqueous carbonate-bearing streams with pH > 8 are produced by contacting fresh water and carbon dioxide with various ion-exchange materials (e.g., Na form zeolites or ion exchange resins). These streams are mixed with produced water containing varying concentrations (~0.01 – 1.0 M) of Ca2+ leading to the precipitation of solid calcium carbonate (PCC). This process has the advantages of using regenerable solids in a simple and continuous process to increase the pH of water by ion exchange instead of relying on the consumption of costly and unsustainable sources of alkalinity (e.g., sodium hydroxide). While once-through column experiments showed the above benefits, the same were yet to established in a steady-state process with recycle streams. In this work, we set up a process simulation to quantify the energy requirements and CO2 emissions associated with the process and seek optimal produced water compositions and CO2 concentrations (5 – 20 vol%). The process simulation was set up in ASPEN Plus using eRNTL as the thermodynamic property method and sequential modular strategy. Ion exchange alkaline solution was simulated using sodium hydroxide and validated against the experimental data obtained from once-through kinetic experiments. Nanofiltration and reverse osmosis membrane steps were also implemented for the separation of divalent cations and production of fresh water and a regeneration stream following mineralization. Sensitivity analysis was carried out using a range of produced water compositions (0.01 – 1.0 M Ca2+, 0.001 – 0.15 M Mg2+, 0.5 – 3.5 M Na+ and 0.0004 – 0.002 M Fe2+) according to the United States Geological Survey (USGS) database. Calcium carbonate yields increased with increasing CO2 concentrations and were maximized using produced water compositions with larger Ca2+ concentrations. Maximum calcium carbonate yields produced at 5 vol%, 12 vol% and 20 vol% CO2 were 2.3 mmol/L, 5.5 mmol/L, and 9.3 mmol/L, respectively, with the formation of brucite (a magnesium hydroxide phase, Mg(OH)2) and goethite (an iron hydroxide phase, FeOOH) as the primary contaminant phases (99% calcite, 0.6% brucite, 0.4% goethite), which agree with phases detected by XRD experimentally. These results indicate high purity calcium carbonate can be precipitated using industrial waste streams. Consequentially, energy consumption and net CO2 emissions were minimized where precipitated calcium carbonate was maximized for all produced water compositions and CO2 concentrations. Minimum energy consumptions were 0.21 kWh/ton CO2 processed, with 98% of the energy input required coming from the membrane filtration steps. Produced water compositions with large Na+ concentrations (> 0.5 M) were effective at reducing energy consumptions due to faster regeneration time of ion exchange materials. Additionally, calculated net CO2 emissions were negative for the process and ranged from -0.02 kg/ton CO2 to -0.15 kg/ton CO2 processed, indicating a low emission process. We will also present techno-economic assessment showing the economic benefits of the current process as an alternative to the addition of stoichiometric bases to induce alkalinity for the precipitation of CaCO3.

Simonetti, Dante↗