BASELINE MEMBRANE SELECTION AND CHARACTERIZATION FOR AN SDE

Thermochemical processes are being developed to provide global-scale quantities of hydrogen. A variant on sulfur-based thermochemical cycles is the Hybrid Sulfur (HyS) Process which uses a sulfur dioxide depolarized electrolyzer (SDE) to produce the hydrogen. In FY05 and FY06, testing at the Savannah River National Laboratory (SRNL) explored a low temperature fuel cell design concept for the SDE. The advantages of this design concept include high electrochemical efficiency and small footprint that are crucial for successful implementation on a commercial scale. A key component of the SDE is the ion conductive membrane through which protons produced at anode migrate to the cathode and react to produce hydrogen. An ideal membrane for the SDE should have both low ionic resistivity and low sulfur dioxide transport. These features allow the electrolyzer to perform at high currents with low potentials, along with preventing contamination of both the hydrogen output and poisoning of the catalysts involved. Another key component is the electrocatalyst material used for the anode and cathode. Good electrocatalysts should be chemically stable and have a low overpotential for the desired electrochemical reactions. This report summarizes results from activities to evaluate commercial and experimental membranes for the SDE. Several different types of commercially-available membranes were analyzed for sulfur dioxide transport as a function of acid strength including perfluorinated sulfonic acid (PFSA), sulfonated poly-etherketone-ketone, and poly-benzimidazole (PBI) membranes. Experimental membranes from the sulfonated diels-alder polyphenylenes (SDAPP) and modified Nafion{reg_sign} 117 were evaluated for SO{sub 2} transport as well. These membranes exhibited reduced transport coefficient for SO{sub 2} transport without the loss in ionic conductivity. The use of Nafion{reg_sign} with EW 1100 is recommended for the present SDE testing due to the limited data regarding chemical and mechanical stability of experimental membranes. Development of new composite membranes by incorporating metal particles or by forming multilayers between PFSA membranes and hydrocarbon membranes will provide methods that will meet the SDE targets (SO{sub 2} transport reduction by a factor of 100) while decreasing catalyst layer delamination and membrane resistivity

COMPONENT DEVELOPMENT NEEDS FOR THE HYBRID SULFUR ELECTROLYZER

Fiscal year 2008 studies in electrolyzer component development have focused on the characterization of membrane electrode assemblies (MEA) after performance tests in the single cell electrolyzer, evaluation of electrocatalysts and membranes using a small scale electrolyzer and evaluating the contribution of individual cell components to the overall electrochemical performance. Scanning electron microscopic (SEM) studies of samples taken from MEAs testing in the SRNL single cell electrolyzer test station indicates a sulfur-rich layer forms between the cathode catalyst layer and the membrane. Based on a review of operating conditions for each of the MEAs evaluated, we conclude that the formation of the layer results from the reduction of sulfur dioxide as it passes through the MEA and reaches the catalyst layer at the cathode-membrane interface. Formation of the sulfur rich layer results in partial delamination of the cathode catalyst layer leading to diminished performance. Furthermore we believe that operating the electrolyzer at elevated pressure significantly increases the rate of formation due to increased adsorption of hydrogen on the internal catalyst surface. Thus, identification of a membrane that exhibits much lower transport of sulfur dioxide is needed to reduce the quantity of sulfur dioxide that reaches the cathode catalyst and is reduced to produce the sulfur-rich layer. Three candidate membranes are currently being evaluated that have shown promise from preliminary studies, (1) modified Nafion{reg_sign}, (2) polybenzimidazole (PBI), and (3) sulfonated Diels Alder polyphenylene (SDAPP). Testing examined the activity for the sulfur dioxide oxidation of platinum (Pt) and platinum-alloy catalysts in 30 wt% sulfuric acid solution. Linear sweep voltammetry showed an increase in activity when catalysts in which Pt is alloyed with non-noble transition metals such as cobalt and chromium. However when Pt is alloyed with noble metals, such as iridium or ruthenium, the kinetic activity decreases. We recommend further testing to determine if these binary alloys will provide the increased reaction kinetic needed to meet the targets. We also plan to test the performance of these catalyst materials for both proton and sulfur dioxide reduction. The latter may provide another parameter by which we can control the reduction of sulfur dioxide upon transport to the cathode catalyst surface. A small scale electrolyzer (2 cm{sup 2}) has been fabricated and successfully installed as an additional tool to evaluate the effect of different operating conditions on electrolyzer and MEA performance. Currently this electrolyzer is limited to testing at temperatures up to 80 C and at atmospheric pressure. Selected electrochemical performance data from the single cell sulfur dioxide depolarized electrolyzer were analyzed with the aid of an empirical equation which takes into account the overpotential of each of the components. By using the empirical equation, the performance data was broken down into its components and a comparison of the potential losses was made. The results indicated that for the testing conditions of 80 C and 30 wt% sulfuric acid, the major overpotential contribution ({approx}70 % of all losses) arise from the slow reaction rate of oxidation of sulfur dioxide. The results indicate that in order to meet the target of hydrogen production at 0.5 A/cm{sup 2} at 0.6 V and 50 wt% sulfuric acid, identification of a better catalyst for sulfur dioxide oxidation will provide the largest gain in electrolyzer performance

METHOD TO PREVENT SULFUR ACCUMULATION INSIDE MEMBRANE ELECTRODE ASSEMBLY

HyS is conceptually the simplest of the thermochemical cycles and involves only sulfur chemistry. In the HyS Cycle hydrogen gas (H{sub 2}) is produced at the cathode of the electrochemical cell (or electrolyzer). Sulfur dioxide (SO{sub 2}) is oxidized at the anode to form sulfuric acid (H{sub 2}SO{sub 4}) and protons (H{sup +}) as illustrated below. A separate high temperature reaction decomposes the sulfuric acid to water and sulfur dioxide which are recycled to the electrolyzers, and oxygen which is separated out as a secondary product. The electrolyzer includes a membrane that will allow hydrogen ions to pass through but block the flow of hydrogen gas. The membrane is also intended to prevent other chemical species from migrating between electrodes and undergoing undesired reactions that could poison the cathode or reduce overall process efficiency. In conventional water electrolysis, water is oxidized at the anode to produce protons and oxygen. The standard cell potential for conventional water electrolysis is 1.23 volts at 25 C. However, commercial electrolyzers typically require higher voltages ranging from 1.8 V to 2.6 V [Kirk-Othmer, 1991]. The oxidation of sulfur dioxide instead of water in the HyS electrolyzer occurs at a much lower potential. For example, the standard cell potential for sulfur dioxide oxidation at 25 C in 50 wt % sulfuric acid is 0.29 V [Westinghouse, 1980]. Since power consumption by the electrolyzers is equal to voltage times current, and current is proportional to hydrogen production, a large reduction in voltage results in a large reduction in electrical power cost per unit of hydrogen generated

Atomic-resolution spectroscopic imaging of ensembles of nanocatalyst particles across the life of a fuel cell

The thousandfold increase in data-collection speed enabled by aberration-corrected optics allows us to overcome an electron microscopy paradox - how to obtain atomic-resolution chemical structure in individual nanoparticles, yet record a statistically significant sample from an inhomogeneous population. This allowed us to map hundreds of Pt-Co nanoparticles to show atomic-scale elemental distributions across different stages of the catalyst aging in a proton-exchange-membrane fuel cell, and relate Pt-shell thickness to treatment, particle size, surface orientation, and ordering.Comment: 28 pages, 5 figures, accepted, nano letter

PT AND PT/NI "NEEDLE" ELETROCATALYSTS ON CARBON NANOTUBES WITH HIGH ACTIVITY FOR THE ORR

Platinum and platinum/nickel alloy electrocatalysts supported on graphitized (gCNT) or nitrogen doped carbon nanotubes (nCNT) are prepared and characterized. Pt deposition onto carbon nanotubes results in Pt 'needle' formations that are 3.5 nm in diameter and {approx}100 nm in length. Subsequent Ni deposition and heat treatment results in PtNi 'needles' with an increased diameter. All Pt and Pt/Ni materials were tested as electrocatalysts for the oxygen reduction reaction (ORR). The Pt and Pt/Ni catalysts showed excellent performance for the ORR, with the heat treated PtNi/gCNT (1.06 mA/cm{sup 2}) and PtNi/nCNT (0.664 mA/cm{sup 2}) showing the highest activity

EFFECT OF FUEL IMPURITIES ON FUEL CELL PERFORMANCE AND DURABILITY

A fuel cell is an electrochemical energy conversion device that produces electricity during the combination of hydrogen and oxygen to produce water. Proton exchange membranes fuel cells are favored for portable applications as well as stationary ones due to their high power density, low operating temperature, and low corrosion of components. In real life operation, the use of pure fuel and oxidant gases results in an impractical system. A more realistic and cost efficient approach is the use of air as an oxidant gas and hydrogen from hydrogen carriers (i.e., ammonia, hydrocarbons, hydrides). However, trace impurities arising from different hydrogen sources and production increases the degradation of the fuel cell. These impurities include carbon monoxide, ammonia, sulfur, hydrocarbons, and halogen compounds. The International Organization for Standardization (ISO) has set maximum limits for trace impurities in the hydrogen stream; however fuel cell data is needed to validate the assumption that at those levels the impurities will cause no degradation. This report summarizes the effect of selected contaminants tested at SRNL at ISO levels. Runs at ISO proposed concentration levels show that model hydrocarbon compound such as tetrahydrofuran can cause serious degradation. However, the degradation is only temporary as when the impurity is removed from the hydrogen stream the performance completely recovers. Other molecules at the ISO concentration levels such as ammonia don't show effects on the fuel cell performance. On the other hand carbon monoxide and perchloroethylene shows major degradation and the system can only be recovered by following recovery procedures

EFFECT OF PRETREATMENT ON PT-CO/C CATHODE CATALYSTS FOR THE OXYGEN-REDUCTION REACTION

Carbon supported Pt and Pt-Co electrocatalysts for the oxygen reduction reaction in low temperature fuel cells were prepared by the reduction of the metal salts with sodium borohydride and sodium formate. The effect of surface treatment with nitric acid on the carbon surface and Co on the surface of carbon prior to the deposition of Pt was studied. The catalysts where Pt was deposited on treated carbon the ORR reaction preceded more through the two electron pathway and favored peroxide production, while the fresh carbon catalysts proceeded more through the four electron pathway to complete the oxygen reduction reaction. NaCOOH reduced Pt/C catalysts showed higher activity that NaBH{sub 4} reduced Pt/C catalysts. It was determined that the Co addition has a higher impact on catalyst activity and active surface area when used with NaBH{sub 4} as reducing agent as compared to NaCOOH

CLOSE-OUT REPORT FOR HYS ELECTROLYZER COMPONENT DEVELOPMENT WORK AT SAVANNAH RIVER NATIONAL LABORATORY

The chemical stability, sulfur dioxide transport, ionic conductivity, and electrolyzer performance have been measured for several commercially available and experimental proton exchange membranes (PEMs) for use in a sulfur dioxide depolarized electrolyzer (SDE). The SDE's function is to produce hydrogen by using the Hybrid Sulfur (HyS) Process, a sulfur based electrochemical/thermochemical hybrid cycle. Membrane stability was evaluated using a screening process where each candidate PEM was heated at 80 C in 63.5 wt. % H{sub 2}SO{sub 4} for 24 hours. Following acid exposure, chemical stability for each membrane was evaluated by FTIR using the ATR sampling technique. Membrane SO{sub 2} transport was evaluated using a two-chamber permeation cell. SO{sub 2} was introduced into one chamber whereupon SO{sub 2} transported across the membrane into the other chamber and oxidized to H{sub 2}SO{sub 4} at an anode positioned immediately adjacent to the membrane. The resulting current was used to determine the SO{sub 2} flux and SO{sub 2} transport. Additionally, membrane electrode assemblies (MEAs) were prepared from candidate membranes to evaluate ionic conductivity and selectivity (ionic conductivity vs. SO{sub 2} transport) which can serve as a tool for selecting membranes. MEAs were also performance tested in a HyS electrolyzer measuring current density versus a constant cell voltage (1V, 80 C in SO{sub 2} saturated 30 wt% H{sub 2}SO{sub 4}). Finally, candidate membranes were evaluated considering all measured parameters including SO{sub 2} flux, SO{sub 2} transport, ionic conductivity, HyS electrolyzer performance, and membrane stability. Candidate membranes included both PFSA and non-PFSA polymers and polymer blends of which the non-PFSA polymers, BPVE-6F and PBI, showed the best selectivity. Testing examined the activity for the sulfur dioxide oxidation of platinum base electrocatalyst in 30 wt% sulfuric acid solution. Linear sweep voltammetry showed an increase in activity when catalysts in which Pt is alloyed with non-noble transition metals such as cobalt, chromium and iron. However when Pt is alloyed with noble metals, such as iridium or ruthenium, the kinetic activity as well as the stability decreases

EVALUATION OF PROTON-CONDUCTING MEMBRANES FOR USE IN A SULFUR-DIOXIDE DEPOLARIZED ELECTROLYZER

The chemical stability, sulfur dioxide transport, ionic conductivity, and electrolyzer performance have been measured for several commercially available and experimental proton exchange membranes (PEMs) for use in a sulfur dioxide depolarized electrolyzer (SDE). The SDE's function is to produce hydrogen by using the Hybrid Sulfur (HyS) Process, a sulfur based electrochemical/thermochemical hybrid cycle. Membrane stability was evaluated using a screening process where each candidate PEM was heated at 80 C in 60 wt. % H{sub 2}SO{sub 4} for 24 hours. Following acid exposure, chemical stability for each membrane was evaluated by FTIR using the ATR sampling technique. Membrane SO{sub 2} transport was evaluated using a two-chamber permeation cell. SO{sub 2} was introduced into one chamber whereupon SO{sub 2} transported across the membrane into the other chamber and oxidized to H{sub 2}SO{sub 4} at an anode positioned immediately adjacent to the membrane. The resulting current was used to determine the SO{sub 2} flux and SO{sub 2} transport. Additionally, membrane electrode assemblies (MEAs) were prepared from candidate membranes to evaluate ionic conductivity and selectivity (ionic conductivity vs. SO{sub 2} transport) which can serve as a tool for selecting membranes. MEAs were also performance tested in a HyS electrolyzer measuring current density versus a constant cell voltage (1V, 80 C in SO{sub 2} saturated 30 wt% H2SO{sub 4}). Finally, candidate membranes were evaluated considering all measured parameters including SO{sub 2} flux, SO{sub 2} transport, ionic conductivity, HyS electrolyzer performance, and membrane stability. Candidate membranes included both PFSA and non-PFSA polymers and polymer blends of which the non-PFSA polymers, BPVE-6F and PBI, showed the best selectivity

Fiscal Year 2008

This report summarizes results from all of the membrane testing completed to date at the Savannah River National Laboratory (SRNL) for the sulfur dioxide-depolarized electrolyzer (SDE). Several types of commercially-available membranes have been analyzed for ionic resistance and sulfur dioxide transport including perfluorinated sulfonic acid (PFSA), sulfonated polyether-ketone-ketone (SPEKK), and polybenzimidazole membranes (PBI). Of these membrane types, the poly-benzimidazole membrane, Celtec-L, exhibited the best combination of characteristics for use in an SDE. Several experimental membranes have also been analyzed including hydrated sulfonated Diels-Alder polyphenylenes (SDAPP) membranes from Sandia National Laboratory, perfluorosulfonimide (PFSI) and sulfonated perfluorocyclobutyl aromatic ether (S-PFCB) prepared by Clemson University, hydrated platinum-treated PFSA prepared by Giner Electrochemical Systems (GES) and Pt-Nafion{reg_sign} 115 composites prepared at SRNL. The chemical stability, SO{sub 2} transport and ionic conductivity characteristics have been measured for several commercially available and experimental proton-conducting membranes. Commercially available PFSA membranes such as the Nafion{reg_sign} series exhibited excellent chemical stability and ionic conductivity in sulfur dioxide saturated sulfuric acid solutions. Sulfur dioxide transport in the Nafion{reg_sign} membranes varied proportionally with the thickness and equivalent weight of the membrane. Although the SO{sub 2} transport in the Nafion{reg_sign} membranes is higher than desired, the excellent chemical stability and conductivity makes this membrane the best commercially-available membrane at this time. Initial results indicated that a modified Nafion{reg_sign} membrane incorporating Pt nanoparticles exhibited significantly reduced SO{sub 2} transport. Reduced SO{sub 2} transport was also measured with commercially available PBI membrane and several experimental membranes produced at SNL and Clemson. These membranes also exhibit good chemical stability and conductivity in concentrated sulfuric acid solutions and, thus, serve as promising candidates for the SDE. Therefore, we recommend further testing of these membranes including electrolyzer testing to determine if the reduced SO{sub 2} transport eliminates the formation of sulfur-containing films at the membrane/cathode interface. SO{sub 2} transport measurements in the custom built characterization cell identified experimental limitations of the original design. During the last quarter of FY08 we redesigned and fabricated a new testing cell to overcome the previous limitations. This cell also offers the capability to test membranes under polarized conditions as well as test the performance of MEAs under selected electrolyzer conditions