GEMINI FUEL CELL POWER SOURCE - FIRST SPACECRAFT APPLICATION
Design and development of the ion-exchange membrane fuel cell intended to furnish electric power and drinking water to the gemini spacecraft
ION EXCHANGE↗
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A fuel cell energy storage system for Space Station extravehicular activity
The development of a fuel cell energy storage system for the Space Station Extravehicular Mobility Unit (EMU) is discussed. The ion-exchange membrane fuel cell uses hydrogen stored as a metal hydride. Several features of the hydrogen-oxygen fuel cell are examined, including its construction, hydrogen storage, hydride recharge, water heat, water removal, and operational parameters.
Rosso, Matthew J., Jr.↗
Challenges to the Transition of IPMC Artificial Muscle Actuators to Practical Application
Ion-exchange membrane metallic composites (IPMC), which were first reported in 1992, are one of the electroactive materials (EAP) with potential applications as artificial muscle actuators. The recent introduction of perfluorocarboxylate-gold composite with tetra-n-butylammonium and Lithium cations instead of sodium made the most significant improvement of the material electroactivity. Under less than 3 volts, IPMC with the new constituents is capable of bending beyond a complete loop. Taking into account the fact that IMPC materials do not induce a significant force, the authors are extensively seeking applications for these bending EAP. Some of the applications that were demonstrated include dust-wiper, catheter guide, miniature motor, robotic-gripper, micro-manipulator, etc. Generally, space applications are the most demanding in terms of operating conditions, robustness and durability, and the co-authors of this paper are jointly addressing the associated challenges. Specifically, a dust-wiper is being developed for the Nanorover's infrared camera window of the MUSES-CN mission. This joint NASA and the Japanese space agency mission, is scheduled to be launch from Kagoshima, Japan, in January 2002, to explore the surface of a small near-Earth asteroid. Several issues that are critical to the operation of IPMC are addressed including the operation in vacuum, low temperatures, and the effect of the electromechanical characteristic of the IPMC on its actuation capability. Highly efficient IPMC materials, mechanical modeling, unique elements and protective coating were introduced by the authors and are making a high probability the success of the IPMC actuated dust-wiper.
Bar-Cohen, Yoseph↗
Monitored separation device
A device for separating and purifying useful quantities of particles comprises: a. an anolyte reservoir connected to an anode, the anolyte reservoir containing an electrophoresis buffer; b. a catholyte reservoir connected to a cathode, the catholyte reservoir also containing the electrophoresis buffer; c. a power supply connected to the anode and to the cathode; d. a column having a first end inserted into the anolyte reservoir, a second end inserted into the catholyte reservoir, and containing a separation medium; e. a light source; f. a first optical fiber having a first fiber end inserted into the separation medium, and having a second fiber end connected to the light source; g. a photo detector; h. a second optical fiber having a third fiber end inserted into the separation medium, and having a fourth fiber end connected to the photo detector; and i. an ion-exchange membrane in the anolyte reservoir.
Jackson, George William↗
Method for Monitored Separation and Collection of Biological Materials
A device for separating and purifying useful quantities of particles comprises: (a) an anolyte reservoir connected to an anode, the anolyte reservoir containing an electrophoresis buffer; (b) a catholyte reservoir connected to a cathode, the catholyte reservoir also containing the electrophoresis buffer; (c) a power supply connected to the anode and to the cathode; (d) a column having a first end inserted into the anolyte reservoir, a second end inserted into the catholyte reservoir, and containing a separation medium; (e) a light source; (f) a first optical fiber having a first fiber end inserted into the separation medium, and having a second fiber end connected to the light source; (g) a photo detector; (h) a second optical fiber having a third fiber end inserted into the separation medium, and having a fourth fiber end connected to the photo detector; and (i) an ion-exchange membrane in the anolyte reservoir.
Jackson, George William↗
Silver Ion Biocide Delivery System for Water Disinfection
U.S. space exploration missions have long considered returning to the Moon and exploration of Mars that challenge life support systems. For these long duration missions, there is interest in replacing the iodine water treatment system with ionic silver, a proven biocide. For long duration exploration missions, it is imperative that an effective biocide be used that prevents microbial growth, biofilm formation, and microbially induced corrosion in the water storage and distribution systems while minimizing logistical supply requirements associated with the biocide delivery system. Two biocide delivery systems have been developed that electrochemically produce silver ions for disinfecting water throughout the water storage and distribution system. One system uses a newly developed hybrid micro-filtration and ion-exchange membrane to produce an abundance of silver ions at the 1000 ppb level upstream in the water distribution system to prevent biofilm growth. This is followed by a downstream collection module that electrochemically removes these silver ions before the water is discharged. Another approach uses a membraneless reactor to produce a 1000 ppb silver ion concentration level that also has a mechanically driven electrode cleaning mechanism that removes oxide films ensuring long life operation. By maintaining a sufficiently high level of silver ions throughout the water storage and distribution system, biofilm formation is suppressed. This approach overcomes present concerns where spurious silver deposition occurs on the container and flow line surfaces thus lowering the silver ion concentration to unsatisfactory disinfection levels.
Slote, Benjamin M.↗
Complexation-driven ion-exchange polymer inclusion membranes for separation of cobalt and nickel ions from lithium-ion via proton pumping
Separation of Co 2+ and Ni 2+ from Li + using an ion exchange polymer inclusion membrane.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Understanding and controlling the fundamental photochemistry of protonic solar energy conversion (Final Scientific/Technical Report)
The selectivity and activity of most fuel-forming reactions are tunable by the concentration of electrons, holes, protons, and/or hydroxides. That is one reason why traditional solar energy conversion processes are used to drive these reactions, where light directly increases the concentration of electrons and holes. We, instead, took a different approach, using light to increase the concentration of protons and/or hydroxides. For this, we leveraged photophysical and solid-state physics theories, techniques, and design strategies previously developed for the study of traditional solar energy conversion processes. We designed and fabricated several materials platforms based on molecular photoacid and photobase dyes coupled with ion-exchange polymer membranes and assessed their fundamental photoelectrochemistry. We demonstrated control over built-in electric potentials, photovoltages, proton-transfer kinetics, and efficiency limits to our approach. Understanding the basic science of these dye-sensitized protonic membranes and their photochemical mechanisms is of use to the DOE-relevant processes of solar photochemical fuel formation, solar photodialytic desalination, and solar cells. Moreover, functional materials that we developed from this project may be of use to several broad-reaching fields and may provide the foundation for a completely new, inexpensive, and robust solar energy conversion technology.
14 SOLAR ENERGY↗
Selective concentration of multivalent cations via electrodialysis through tandem membranes
Selective electrodialysis is attractive for recovering and recycling valuable ions. However, most studies in this field focus on membranes that are selective for monovalent ions. Multivalent cations preferentially partition into cation-exchange membranes, but low mobilities and concentration polarization limit electrodialysis selectivities for these cations. This work employs electrodialysis through an “in-series” combination of a Nafion membrane and a multilayer polyelectrolyte film (MPF)-coated Nafion membrane to concentrate and isolate La 3+ or Mg 2+ from monovalent ions. The bare Nafion membrane gives a La 3+ /Na + selectivity up to 4 (depending on conditions), which enables concentration of La 3+ with a high current efficiency. The MPF-coated membrane allows selective passage of Na + while rejecting La 3+ to increase the purity of the concentrated multivalent cation. For example, the concentration of La 3+ in the accumulation solution can reach 9 times its original concentration in the feed solution with a purity of 93 mol% (99 wt%) when starting with equimolar mixtures of NaNO 3 and La(NO 3 ) 3 . This study examines how the separation varies with the type of polyelectrolyte, the applied voltage, and the composition of feed, accumulation, and cathode solutions. Here, a high nitric acid concentration (0.5 M) in the cathode compartment allows monovalent anions to pass through the MPF-coated Nafion membrane to maintain the electroneutrality of the accumulation solution. With a low acid concentration (0.04 M) in the cathode chamber, water splitting occurs at the MPF-coated membrane and La(OH) 3 precipitates.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Self‐Assembled Membranes for High Ion Selectivity and Proton Blocking in Electrochemical Applications
Anion-exchange membranes (AEMs) with high anion/cation selectivity and exceptional proton-blocking ability are critical for applications such as bipolar membrane electrodialysis and electrochemical acid recovery. However, existing AEMs are constrained by a trade-off between ionic conductivity and selectivity, largely due to the intrinsic coupling between charge density and water content, and they suffer from excessive proton leakage facilitated by the Grotthuss hopping mechanism. In this work, poly(vinylimidazolium) membranes functionalized with long alkyl side chains that self-assemble into well-defined microphase-separated morphologies stabilized by hydrophobic and electrostatic interactions are reported. These unique structures localize the charge density along the polymer backbone to promote fast and selective ion transport. As a result, these membranes exhibit ionic conductivities and counter-ion diffusivities surpassing those of conventional homogeneous membranes, along with unprecedented counter-ion/co-ion selectivity and proton-blocking ability. These results establish a new design paradigm for high-performance, phase separated charged polymer membranes that overcome the limitations of homogeneous membranes, with broad implications for advanced electrochemical technologies.
36 MATERIALS SCIENCE↗
Challenges to the Application of IPMC as Actuators of Planetary Mechanisms
Ion-exchange polymer membrane metallic composites (IPMC) are one of the electroactive polymers (EAP) that were shown to have potential application as actuators.
Electroactive↗
Improved Cathode Structure for a Direct Methanol Fuel Cell
An improved cathode structure on a membrane/electrode assembly has been developed for a direct methanol fuel cell, in a continuing effort to realize practical power systems containing such fuel cells. This cathode structure is intended particularly to afford better cell performance at a low airflow rate. A membrane/electrode assembly of the type for which the improved cathode structure was developed (see Figure 1) is fabricated in a process that includes brush painting and spray coating of catalyst layers onto a polymer-electrolyte membrane and onto gas-diffusion backings that also act as current collectors. The aforementioned layers are then dried and hot-pressed together. When completed, the membrane/electrode assembly contains (1) an anode containing a fine metal black of Pt/Ru alloy, (2) a membrane made of Nafion 117 or equivalent (a perfluorosulfonic acid-based hydrophilic, proton-conducting ion-exchange polymer), (3) a cathode structure (in the present case, the improved cathode structure described below), and (4) the electrically conductive gas-diffusion backing layers, which are made of Toray 060(TradeMark)(or equivalent) carbon paper containing between 5 and 6 weight percent of poly(tetrafluoroethylene). The need for an improved cathode structure arises for the following reasons: In the design and operation of a fuel-cell power system, the airflow rate is a critical parameter that determines the overall efficiency, cell voltage, and power density. It is desirable to operate at a low airflow rate in order to obtain thermal and water balance and to minimize the size and mass of the system. The performances of membrane/electrode assemblies of prior design are limited at low airflow rates. Methanol crossover increases the required airflow rate. Hence, one way to reduce the required airflow rate is to reduce the effect of methanol crossover. Improvement of the cathode structure - in particular, addition of hydrophobic particles to the cathode - has been demonstrated to mitigate the effects of crossover and decrease the airflow required.
Valdez, Thomas↗
Dual membrane hollow fiber fuel cell and method of operating same
A gaseous fuel cell is described which includes a pair of electrodes formed by open-ended, ion-exchange hollow fibers, each having a layer of metal catalyst deposited on the inner surface and large surface area current collectors such as braided metal mesh in contact with the metal catalyst layer. A fuel cell results when the electrodes are immersed in electrolytes and electrically connected. As hydrogen and oxygen flow through the bore of the fibers, oxidation and reduction reactions develop an electrical potential. Since the hollow fiber configuration provides large electrode area per unit volume and intimate contact between fuel and oxidizer at the interface, and due to the low internal resistance of the electrolyte, high power densities can be obtained.
Ingham, J. D.↗
Influence of CO 2 -Regenerative Film Properties in Enhancing C 2+ Products Selectivity While Mitigating CO 2 Crossover
Zero-gap anion-exchange membrane electrode assembly (AEMEA) electrolyzers operating in alkaline media face challenges such as CO 2 crossover and salting-out. The bipolar membrane electrode assembly (BPMEA) electrolyzer, using DI water as the electrolyte, addresses both CO 2 crossover and salting-out issues. As cations, which are crucial in stabilizing the CO 2 R intermediates, are absent in the electrolyte, cations embedded in the AEM play an important role in dictating the CO 2 R selectivity and activity in BPMEA systems. So far, no systematic study has been conducted on the influence of cations embedded in AEMs on CO 2 selectivity and activity in BPMEA systems. Moreover, BPMEA systems impose an additional challenge: low stability due to delamination of the bipolar membrane caused by CO 2 regeneration at the membrane-membrane interface. To enhance the stability of the electrolyzer, a simple yet highly reproducible strategy for coating a porous CO 2 regenerative film on smooth Nafion 117 is demonstrated in this work, along with a systematic study of four different commercially available AEMs, composed of different cations and cation densities, for use in combination with Nafion 117 and copper catalyst at the cathode. We found that the PiperION membrane delivers selectivity and activity comparable to those of alkali-metal cations, owing to the enhanced local electric field resulting from the combined effects of a high positive charge on the N atom of the piperidinium cation and the high ion-exchange capacity. Further, we studied the influence of the thickness of the PiperION porous layer over Nafion 117 on CO 2 R selectivity and found that 70 μm is the minimum thickness to achieve maximum C 2+ products selectivity, reduced the CO 2 crossover to 5% from 25% at 4 SCCM and 150 mA cm –2 , and was stable for operation beyond 100 h. The selectivity of this system, compared with AEMEA, and stability outperformed both AEMEA and BPMEA. This study helps design more effective BPMs to inhibit CO 2 crossover while enabling stable and selective electrochemical CO 2 reduction to C 2+ hydrocarbons.
Cations↗
Comparison of the Effects of Bipolar Membrane Preparation Conditions on the Mechanical Durability and Electrochemical Performance for Electrodialysis Applications
Bipolar membranes (BPMs) are enabling materials for electrochemical conversion technologies such as water electrolysis, fuel cells, CO 2 electrolysis, and electrodialysis (ED) for direct air/ocean capture of CO 2 . However, current BPM durability can suffer from chemical, mechanical, and performance degradation when operated at high current density (ion flux) and physical scale. Therefore, this limits its adoption in a wider applications space. BPMs have several known degradation mechanisms, including chemical breakdown of ion-exchange polymers, loss of junction adhesion, or physical breakdown due to shearing force and pressure swings in an electrodialysis cell. To assess the electrochemical stability and mechanical durability of BPMs under operational conditions, we investigated how fabrication conditions (including preconditioning, hot-pressing temperature and pressure, and catalyst loading) impact the adhesion of custom-made BPMs. T-peel studies were performed ex situ to quantify adhesive forces of BPMs, and bipolar membrane electrodialysis (BPMED) experiments were performed to assess the electrochemical performance of the corresponding BPMs. The results of this systematic comparison indicate that hydration and heated pressing create improved adhesion during the fabrication of BPMs, and BPMED testing shows that these fabrication techniques are not detrimental to the electrochemical performance of the BPMs.
36 MATERIALS SCIENCE↗
The ferredoxin-thioredoxin system of a green alga, Chlamydomonas reinhardtii: identification and characterization of thioredoxins and ferredoxin-thioredoxin reductase components
The components of the ferredoxin-thioredoxin (FT) system of Chlamydomonas reinhardtii have been purified and characterized. The system resembled that of higher plants in consisting of a ferredoxin-thioredoxin reductase (FTR) and two types of thioredoxin, a single f and two m species, m1 and m2. The Chlamydomonas m and f thioredoxins were antigenically similar to their higher-plant counterparts, but not to one another. The m thioredoxins were recognized by antibodies to both higher plant m and bacterial thioredoxins, whereas the thioredoxin f was not. Chlamydomonas thioredoxin f reacted, although weakly, with the antibody to spinach thioredoxin f. The algal thioredoxin f differed from thioredoxins studied previously in behaving as a basic protein on ion-exchange columns. Purification revealed that the algal thioredoxins had molecular masses (Mrs) typical of thioredoxins from other sources, m1 and m2 being 10700 and f 11500. Chlamydomonas FTR had two dissimilar subunits, a feature common to all FTRs studied thus far. One, the 13-kDa ("similar") subunit, resembled its counterpart from other sources in both size and antigenicity. The other, 10-kDa ("variable") subunit was not recognized by antibodies to any FTR tested. When combined with spinach, (Spinacia oleracea L.) thylakoid membranes, the components of the FT system functioned in the light activation of the standard target enzymes from chloroplasts, corn (Zea mays L.) NADP-malate dehydrogenase (EC 1.1.1.82) and spinach fructose 1,6-bisphosphatase (EC 3.1.3.11) as well as the chloroplast-type fructose 1,6-bisphosphatase from Chlamydomonas. Activity was greatest if ferredoxin and other components of the FT system were from Chlamydomonas. The capacity of the Chlamydomonas FT system to activate autologous FBPase indicates that light regulates the photosynthetic carbon metabolism of green algae as in other oxygenic photosynthetic organisms.
NASA Discipline Exobiology↗
Kinetic Monte Carlo Framework for Coupled Degradation and Dehydration of Anion Exchange Membranes
Kinetic Monte Carlo (kMC) simulations, augmented with temporal-acceleration schemes, can efficiently handle stiff reaction-transport networks when fast processes rapidly relax to quasi-equilibrium on a fixed lattice. However, in glassy anion-exchange membranes (AEM), rare and irreversible chemical degradation events continuously reshape the nanoscale morphology, and the associated hydration and transport degrees of freedom remain far from a well-defined local equilibrium. This combination of evolving state space and nonequilibrated fast dynamics lies outside the scope of existing kMC acceleration frameworks. Here, to address this challenge, we introduce an auxiliary-particle kinetic Monte Carlo (AP-kMC) scheme. In AP-kMC, short-lived mobile particles spawned at degradation sites execute hop, water-elimination, and decay moves, enforcing rapid local relaxation of the hydration structure while preserving the stochastic rules of kMC. Parameterized with molecular-dynamics morphologies and experimental solution degradation kinetics, AP-kMC reproduces the evolution of ion-exchange capacity, water uptake, and conductivity, and reveals a feedback loop in which poorly hydrated sites degrade first and each degradation event induces further local dehydration. The resulting thinning and fragmentation of water channels cause loss of hydrophilic percolation and abrupt conductivity collapse well before complete charge loss. AP-kMC thus reframes AEM durability as a coupled degradation–drying–percolation problem and provides a transferable strategy to simulate reactive, out-of-equilibrium polymer electrolytes where local solvation controls reactivity.
organic↗
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↗