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At least 127 records · Page 7

Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

Parthasarathy, Arvind↗

Revitalizing interface in protonic ceramic cells by acid etch

Protonic ceramic electrochemical cells hold the promise to be operated at intermediate temperatures below 600 °C. Although the high proton conductivity of the bulk electrolyte has been demonstrated, it cannot be fully utilized in electrochemical full cells due to unknown causes. A practical solution is thus urgently needed. Here we showed that it comes from poor contacts between the low-temperature processed oxygen electrode-electrolyte interface. We demonstrated that a simple acid treatment can effectively rejuvenate the high-temperature annealed electrolyte surface, resulting in reactive bonding between the oxygen electrode and the electrolyte and improved electrochemical performance and stability. This enables exceptional protonic ceramic fuel-cell performance down to 350 °C, with peak power densities of 1.6 W cm -2 at 600 °C, 650 mW cm -2 at 450 °C, and 300 mW cm -2 at 350 °C, as well as stable electrolysis operations at large current densities above 3.9 A cm -2 under 1.4 V applied voltage at 600 °C. Furthermore, our work highlights the critical role of interfacial engineering in ceramic electrochemical devices and offers new understanding and practices towards sustainable energy infrastructure.

08 HYDROGEN↗

A High Performance H2-Cl2 Fuel Cell for Space Power Applications

NASA has numerous airborne/spaceborne applications for which high power and energy density power sources are needed. The proton exchange membrane fuel cell (PEMFC) is an attractive candidate for such a power source. PEMFC's offer many advantages for airborne/spaceborne applications. They have high power and energy densities, convert fuel to electrical power with high efficiency at both part and full load, and can rapidly startup and shutdown. In addition, PEMFC's are lightweight and operate silently. A significant impediment to the attainment of very high power and energy densities by PEMFC's is their current exclusive reliance on oxygen as the oxidant. Conventional PEMFC's oxidize hydrogen at the anode and reduce oxygen at the cathode. The electrode kinetics of oxygen reduction are known to be highly irreversible, incurring large overpotential losses. In addition, the modest open circuit potential of 1.2V for the H2-O2 fuel cell is unattainable due to mixed potential effects at the oxygen electrode. Because of the high overpotential losses, cells using H2 and O2 are capable of achieving high current densities only at very low cell voltages, greatly curtailing their power output. Based on experimental work on chlorine reduction in a gas diffusion electrode, we believe significant increases in both the energy and power densities of PEMFC systems can be achieved by employing chlorine as an alternative oxidant.

Anderson, Everett B.↗

Theoretical Analysis of Critical Conditions for Crack Formation and Propagation, and Optimal Operation of SOECs

A theoretical analysis on crack formation and propagation was performed based on the coupling between the electrochemical process, classical elasticity, and fracture mechanics. The chemical potential of oxygen, thus oxygen partial pressure, at the oxygen electrode-electrolyte interface ( μ O 2 OE∣El ) was investigated as a function of transport properties, electrolyte thickness and operating conditions (e.g., steam concentration, constant current, and constant voltage). Our analysis shows that: a lower ionic area specific resistance (ASR), r i O E , and a higher electronic ASR ( r e O E ) of the oxygen electrode/electrolyte interface are in favor of suppressing crack formation. The μ O 2 O E ∣ E l , thus local pO 2 , are sensitive towards the operating parameters under galvanostatic or potentiostatic electrolysis. Constant current density electrolysis provides better robustness, especially at a high current density with a high steam content. While constant voltage electrolysis leads to greater variations of μ O 2 O E ∣ E l . Constant current electrolysis, however, is not suitable for an unstable oxygen electrode because μ O 2 O E ∣ E l can reach a very high value with a gradually increased r i O E . A crack may only occur under certain conditions when p O 2 T P B > p c r .

42 ENGINEERING↗

Space Electrochemical Research and Technology Conference, 2nd, Cleveland, OH, Apr. 11-13, 1989, Proceedings

Attention is given to topics of advanced concepts, hydrogen-oxygen fuel cells and electrolyzers, nickel electrodes, and advanced rechargeable batteries. Papers are presented on human exploration mission studies, advanced rechargeable sodium batteries with novel cathodes, advanced double-layer capacitors, recent advances in solid-polymer electrolyte fuel cell technology with low platinum loading electrodes, electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications, and the corrosion testing of candidates for the alkaline fuel cell cathode. Other papers are on a structural comparison of nickel electodes and precursor phases, the application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes, advances in lightweight nickel electrode technology, multimission nickel-hydrogen battery cell for the 1990s, a sodium-sulfur battery flight experiment definition study, and advances in ambient-temperature secondary lithium cells.

O'Donnell, Patricia M.↗

Investigation of oxygen evolution reaction with 316 and 304 stainless-steel mesh electrodes in natural seawater electrolysis

Here, two commercially available stainless steel mesh substrates (316 SS and 304 SS) were evaluated as electrodes for oxygen evolution reaction (OER) in natural seawater electrolysis. The results show the 304 SS is less stable against corrosion under neutral (pH of 8.5) and low alkaline (0.1 M NaOH, pH of 12.8) seawater electrolytes because of the direct metal dissolution and chlorine evolution reaction (CER), and the 316 SS is superior to 304 SS in terms of electrocatalytic activity and resistance to corrosion under the same media. The performance of 304 SS is comparable to 316 SS under the high alkaline (1 M NaOH, pH of 13.7) seawater electrolyte, where the CER and metal dissolution are suppressed by OER. The overpotential for 304 and 316 SS is around 430 mV at 10 mA cm -2 , and the Tafel slopes are below 50 mV dec -1 under the high alkaline (1 M NaOH) seawater electrolyte, showing promising performance. The poor resistance to corrosion of 304 SS is attributed to the low Mo content, and it is supposed that the stability of both 304 and 316 SS can be improved further with the addition of Mo content. This work expands on promising substrates for natural seawater electrolysis, with cost and performance advantages.

Stainless-steel mesh↗

The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

A model for chemical reactions in porous molybdenum electrodes is presented which is based on thermochemical and kinetic data, known sodium-molybdenum-oxygen chemistry, X-ray diffraction analysis of molybdenum and molybdenum oxide electrodes, and the electrochemical behavior of the cell. Enhanced sodium transport through the electrode in its optimum performance state is found to be due to the high sodium ion conductivity of molten Na2MoO4 in the pores, and the electrical conduction to the molybdenum matrix by Na2Mo3O6. The decline of electrode performance is shown to be due to a combination of loss mechanisms for the Na-Mo-O compounds including reduction at short circuit, disproportionation of Na2Mo3O6 at open circuit, and the evaporation of Na2MoO4 at elevated temperature. It is suggested that operation of the cell at moderate voltage of about 0.5 V corresponding to maximum power may be a more stable condition for the porous electrode than open-circuit stand or short-circuit, where degradation reactions are heightened.

Williams, R. M.↗

A novel unitized regenerative proton exchange membrane fuel cell

A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed in work performed at Lynntech. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel unitized regenerative fuel cell and results obtained on testing it will be presented.

Murphy, O. J.↗

A Novel Unitized Regenerative Proton Exchange Membrane Fuel Cell

A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel single cell unitized regenerative fuel cell and results obtained on testing it are presented.

Murphy, O. J.↗

Microstructure-based modeling of inner oxygen pressure in solid oxide electrolysis cells: Analysis of electrode delamination and mitigation

One major degradation mechanism during long-term operation of solid oxide electrolysis cells (SOECs) is delamination of oxygen electrodes (OEs). The driving force for the electrode delamination could be the generated high inner oxygen pressure near the electrode-electrolyte interface during operation. However, the effects of transport properties and electrode thickness on the inner oxygen partial pressure are not well understood. Here a microstructure-based electrochemical model, which includes the conduction of electrons and oxygen ions coupled with Butler-Volmer-type chemical reactions at triple-phase-boundaries (TPBs), is employed to investigate the oxygen pressure in lanthanum strontium manganate (LSM)-based SOECs. The model is applied to both two-dimensional (2D) prototype microstructures and three-dimensional (3D) realistic microstructures, and the oxygen pressure is analyzed as a function of transport properties and electrode thickness under both potentiostatic and galvanostatic operations. The simulation results suggest strategies to suppress electrode delamination. The simulation results are compared to an analytical solution, and the discrepancies are attributed to the Butler-Volmer-type kinetics included in the microstructure-based model.

25 ENERGY STORAGE↗

A reversible perovskite air electrode for active and durable oxygen reduction and evolution reactions via the A-site entropy engineering

The performance of reversible solid oxide electrochemical cells (R-SOECs) is largely hindered by the insufficient electroactivity and poor durability of the bifunctional air electrodes, where the oxygen reduction and evolution reactions (ORR and OER) occur. Here, we report our findings in boosting the electrochemical activity and durability of an air electrode with Pr 0.2 Ba 0.2 Sr 0.2 La 0.2 Ca 0.2 CoO 3-δ (PBSLCC) via an A-site entropy engineering. The PBSLCC electrode shows enhanced oxygen reaction activity and excellent durability compared to binary and ternary double perovskites (PrBaCo 2 O 5+δ and Pr 0.8 Ba 0.8 Ca 0.4 Co 2 O 5+δ , respectively). A low and nearly unchanged area-specific resistance of 0.042Ωcm 2 is achieved at 750 °C during the 225-h stability test. La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ electrolyte-supported cells with the PBSLCC air electrode show remarkable performance at 800 °C, demonstrating a peak power density of 1.2Wcm -2 in the fuel cell mode, and a current density of -1.1 Acm -2 at 1.3 V in the electrolysis mode while maintaining the excellent cycling durability of 228 h at ±0.5 Acm -2 under humidified H 2 (10% H 2 O). A bulk oxygen p-band center model is applied to verify that tailoring of the A-site entropy strongly influences the surface exchange coefficients (k* chem ), leading to higher oxygen reaction activity of PBSLCC than the binary and ternary perovskites. Finally, this study opens a new class of high-entropy perovskites for the rational design of air electrodes for R-SOECs with high activity and durability.

30 DIRECT ENERGY CONVERSION↗

Alkali Metal Thermoelectric Conversion (AMTEC) for space nuclear power systems

Performance parameters of the Alkali Metal Thermoelectric Converter (AMTEC) for a 100 kW electric power system have been calculated at four technological levels assuming a heat pipe-cooled nuclear reactor heat source. The most advanced level considered would operate between 1180 K converter temperature and 711 K radiator temperature at 16 percent efficiency, and would weigh 1850 kg with a radiator area of 43 sq m. In addition, electrode research studies for the AMTEC systems have been conducted utilizing an experimental test cell of Bankston et al. (1983) and Mo and several Mo-Ti electrodes. It was found that the Mo-Ti electrodes offered no improvement in lifetime characteristics over the pure Mo electrodes, however, oxygen treatment of a degraded Mo electrode restored its specific power output to 90 percent of its original specific power and maintained this level for 60 hr, thus offering a potential for lifetime stability.

Bankston, C. P.↗

Electrode and Microstructure Dependence of Oxygen Diffusion in Ferroelectric Hafnium Zirconium Oxide Thin Films

Hafnia-based ferroelectrics hold promise to reduce energy demand for computing by enabling compute-in-memory and as non-volatile memories. The ferroelectric phase in this material system is, in part, stabilized by oxygen vacancies. While oxygen vacancies may be a necessity for phase stability, they limit device endurance through diffusion and accumulation into conducting channels. Herein, it is shown that oxygen diffusion is spatially variable within individual grains of ferroelectric hafnium zirconium oxide (HZO). Using 18 O tracers and finite difference modeling, it is shown that grain boundaries and regions near electrode interfaces allow for relatively rapid oxygen diffusion, with values as much as 10 4 larger than the grain cores. Further, the selection of electrode material affects the diffusion coefficients across all microstructural regions. HZO films in contact with TiN electrodes result in more oxygen-deficient HZO films and higher oxygen diffusion coefficients. Tungsten electrodes result in fewer vacancies and lower diffusion coefficients. Diffusion activation energy differences between the HZO with the two electrodes is reconciled by differing populations of charged and uncharged oxygen vacancies. This insight into the local vacancy populations and diffusion pathways provides a platform for designing hafnia-based films, deposition processes, and integration strategies to reduce vacancy gradients and improve performance.

36 MATERIALS SCIENCE↗