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At least 19 records

Effect of structure on current and potential distributions in porous electrode

Porous electrodes generally contain constricted macropores and localized micropores. The effects of the macropore constrictions on the resistance of a capillary were studied and an analytical model was developed for predicting the current distribution in a constricted macropore which directly includes constriction effects and does not require an empirical tortuosity parameter. The current and concentration distributions in localized micropores were also investigated and it was shown that the microporous area is fully accessible to charge and mass transfer processes. From these analyses it was concluded that the micropores primarily affect the kinetics of the interfacial processes by contributing to the interfacial area, while the macropores impose ohmic and mass transport limitations through the volume of the porous electrode.

Lanzi, Oscar

The impedance of a tubular electrode - A model for a porous electrode

A cylindrical tube is used as the basis for a two-dimensional mathematical model to calculate the impedance of a flooded porous electrode. The model incorporates charge-transfer, mass-transfer, and ohmic resistances to obtain the axial and radial dependencies of the concentration and potential profiles. A linearized Butler-Volmer kinetic expression for a simple redox reaction O + e yielding R is used, in conjuction with analytical expressions for the surface concentration and overpotential, to compute the open-circuit impedance. The results of the two-dimensional model, which omits double-layer charging, are compared with the results of a more standardly applied one-dimensional model in which radial variations are neglected, with and without double-layer charging. The simpler-to-apply one-dimensional model is found to be satisfactory when mass-transfer and ohmic resistances are small with respect to charge-transfer resistance. The omission of double-layer charging does not introduce error into the two-dimensional model in the frequency range in which capacitive-like effects are caused by mass-transfer limitations.

Viner, Andrew S.

Modelling of nickel-cadmium batteries using porous electrode theory

A porous electrode modeling technique is discussed which is considered a viable means for quantitatively predicting Ni-Cd cell performance. The authors describe the integration of the cell model into a battery model useful in the design and operation of aerospace applications. Test data from a sealed boilerplate cell are presented for constant current charge and discharge conditions. Performance predictions for similar cases have been performed, and a comparison to the boilerplate data is made. Areas for further development are also noted.

Timmerman, Paul J.

Electrochemical impregnation of nickel hydroxide in porous electrodes

The electrochemical impregnation of nickel hydroxide in porous electrode was investigated both experimentally and theoretically. The loading level and plaque expansion were the most important parameters to be considered. The effects of applied current density, stirring, ratio of solution to electrode volume and pH were identified. A novel flow through electrochemical impregnation is proposed in which the electrolyte is forced through the porous nickel plaque. The thickening of the plaque can be reduced while maintaining high loading capacity. A mathematical model is presented which describes the transport of the nitrate, nickel and hydroxyl ions and the consecutive heterogeneous electrochemical reduction of nitrate and the homogeneous precipitation reaction of nickel hydroxide. The distributions of precipitation rate and active material within the porous electrode are obtained. A semiempirical model is also proposed which takes into account the plugging of the pores.

Ho, Kuo-Chuan

Quantitative local state of charge mapping by operando electrochemical fluorescence microscopy in porous electrodes

We introduce operando quantitative electrochemical fluorescence state of charge mapping (QEFSM), a non-invasive technique to study operating electrochemical systems along with a new design of optically transparent microfluidic redox flow cells compatible with the most demanding optical requirements. QEFSM allows quantitative mappings of the concentration of a particular oxidation state of a redox-active species within a porous electrode during its operation. In this study, we used confocal microscopy to map the fluorescence signal of the reduced form of 2,7-anthraquinone disulfonate (AQDS) in a set of multistep-chronoamperometry experiments. Calibrating these images and incorporating an analytical model of quinhydrone heterodimer formation with no free parameters, and accounting for the emission of each species involved, we determined the local molecular concentration and the state of charge (SOC) fields within a commercial porous electrode during operation. With this method, electrochemical conversion and species advection, reaction and diffusion can be monitored at heretofore unprecedented transverse and axial resolution (1 μm and 25 μm, respectively) at frame rates of 0.5 Hz, opening new routes to understanding local electrochemical processes in porous electrodes. Here, we observed pore-scale SOC inhomogeneities appearing when the fraction of electroactive species converted in a single pass through the electrode becomes large.

42 ENGINEERING

Characterization of reaction kinetics in a porous electrode

A continuum-model approach, analogous to porous electrode theory, was applied to a thin-layer cell of rectangular and cylindrical geometry. A reversible redox couple is assumed, and the local reaction current density is related to the potential through the formula of Hubbard and Anson for a uniformily accessible thin-layer cell. The placement of the reference electrode is also accounted for in the analysis. Primary emphasis is placed on the effect of the solution-phase ohmic potential drop on the voltammogram characteristics. Correlation equations for the peak-potential displacement from E(sup 0 prime) and the peak current are presented in terms of two dimensionless parameters.

Fedkiw, Peter S.

Topology optimization for the full-cell design of porous electrodes in electrochemical energy storage devices

In this paper, we introduce a density-based topology optimization framework to design porous electrodes for maximum energy storage. We simulate the full cell with a model that incorporates electronic potential, ionic potential, and electrolyte concentration. The system consists of three materials, namely pure liquid electrolyte and the porous solids of the anode and cathode, for which we determine the optimal placement. We use separate electronic potentials to model each electrode, which allows interdigitated designs. As a result, a penalization is required to ensure that the anode and cathode do not touch, i.e., causing a short circuit. We compare multiple 2D designs generated for different fixed conditions, e.g. material properties. A 3D design with complex channel and interlocked structure is also created. All optimized designs are far superior to the traditional monolithic electrode design with respect to energy storage metrics. We observe up to a 750% increase in energy storage for cases with slow effective ionic diffusion within the porous electrode.

25 ENERGY STORAGE

Effect of Electro-Sprayed Porous Electrodes on the Performance and Stability of Water Electrolysis

The efficiency of proton exchange membrane water electrolysis (PEMWE) is a critical issue in realizing the production of green hydrogen. Here, the coexistence of three phases in the catalyst layer of PEMWE causes the mass transport limitation at the interfaces between them. In particular, the vigorous production of gaseous hydrogen and oxygen derived from liquid water is generated in the form of bubbles that seriously deactivate the membrane-electrode assembly (MEA). In this study, we investigated the effect of porous structure in the electrode on the efficiency of hydrogen production at high current density, which is highly related to the mass transport limitation. A widely used commercial catalyst (IrO 2 ) were directly coated on the membrane by the electro-spray method. The porous electrodes on the membrane were formed by the charged catalyst particles that repulsed each other due to the electrostatic forces of the particles. Our membrane electrode assembly (MEA) exhibited outstanding electrolysis performances such as 5.3 A cm -2 and 3.2 A cm -2 at 2.0 V and 1.8 V, respectively, which are the highest values compared with the results published in the current studies. In addition to the porosity, it was confirmed that optimum binder contents positively affect the hydrophobicity and contact resistance of MEA. Through a simple porosity-controlled technique, the performance of PEMWE, in which three phases coexist, can be improved by more than 60 %. Accordingly, we expect that our systematic study on the role of porosity in the electrodes opens a new era to efficiently produce green hydrogen.

catalysts

Method of making porous conductive supports for electrodes

Porous conductive supports for electrochemical cell electrodes are made by electroforming thin corrugated nickel foil, and by stacking pieces of the corrugated foil alternatively with pieces of thin flat nickel foil. Corrugations in successive corrugated pieces are oriented at different angles. Adjacent pieces of foil are bonded by heating in a hydrogen atmosphere and then cutting the stack in planes perpendicular to the foils.

Schaer, G. R.

Porous Iron Electrodes Reduce Energy Consumption During Electrocoagulation of a Virus Surrogate: Insights into Performance Enhancements Using Three-Dimensional Neutron Computed Tomography

Electrocoagulation has attracted significant attention as an alternative to conventional chemical coagulation because it is capable of removing a wide range of contaminants and has several potential advantages. In contrast to most electrocoagulation research that has been performed with nonporous electrodes, in this study, we demonstrate energy-efficient iron electrocoagulation using porous electrodes. In batch operation, investigation of the external pore structures through optical microscopy suggested that a low porosity electrode with sparse connection between pores may lead to mechanical failure of the pore network during electrolysis, whereas a high porosity electrode is vulnerable to pore clogging. Electrodes with intermediate porosity, instead, only suffered a moderate surface deposition, leading to electrical energy savings of 21% and 36% in terms of electrocoagulant delivery and unit log virus reduction, respectively. Neutron computed tomography revealed the critical role of electrode porosity in utilizing the electrode’s internal surface for electrodissolution and effective delivery of electrocoagulant to the bulk. Energy savings of up to 88% in short-term operation were obtained with porous electrodes in a continuous flow-through system. Further investigation on the impact of current density and porosity in long-term operation is desired as well as the capital cost of porous electrodes.

42 ENGINEERING

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.

(abstract) Alkali Metal Diffusion Through Porous Metal Electrodes in AMTEC Cells

The mechanisms of mass transport of an alkali metal through porous metal electrodes in alkali metal thermal-to-electric converter AMTEC cells is important in optimizing these high current density devices, but also affords the opportunity to investigate a variety of simple mass transport modes at high temperatures via electrochemical techniques. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes. Quantitative investigations of Na transport through WPt(sub 3.5) via surface or grain boundary diffusion, and K transport through porous Mo electrodes by free molecular flow, over large ranges of temperature have been performed. WPt(sub 3.5) has especially low transport impedance over the 950 to 1200K temperature range. New results are the Na through porous WPt(sub 3.5) and K through porous Mo diffusion rates and mechanisms.

alkali metal mass transport porous metal electrode