Performance optimization of polymer electrolyte membrane fuel cells using the Nelder-Mead algorithm

The direct-search simplex method for function optimization has been adapted to performance optimization of polymer electrolyte membrane fuel cells (PEMFCs). The established method is strongly application oriented and uses only experimentally determined data for optimization. It is not restricted to discrete parameters optimums and does not require the use of third-party software or computational resources. Hence, it is easy to implement in fuel cell testing stations. The optimization consists of finding, for a given fuel cell load, an optimum set of values of the 7 fuel cell operating parameters: the fuel cell temperature, the reactants' stoichiometric ratios, the reactants' inlet relative humidity, and the reactants' outlet pressures, resulting in the highest fuel cell performance. The performance is measured using a scalar function of the operating parameters and the load and can be defined according to needs.Two PEMFC performance functions: the fuel cell voltage and the system-related fuel cell efficiency were optimized using the procedure for practically sized PEMFC stacks of two designs. With respect to the nominal operating conditions defined as optimal for each stack design by its manufacturer, the gains from the optimization procedure were up to over 12% and up to over 7% for the stack voltage and efficiency, respectively. The validation of the procedure involved 5 stack specimens and four laboratories and consistent results were obtained.     

Chlor-alkali electrolysis with oxygen depolarized cathodes: history,present status and future prospects

The historical development, current status and future prospects of chlor-alkali electrolysis with oxygen depolarized cathodes (ODCs) are summarized. Over the last decades, membrane chlor-alkali technology has been optimized to such an extent that no substantial reduction of the energy demand can be expected from further process modifications. However, replacement of the hydrogen evolving cathodes in the classical membrane cells by ODCs allows for reduction of the cell voltage and correspondingly the energy consumption of up to 30%. This replacement requires the development of appropriate cathode materials and novel electrolysis cell designs. Due to their superior long-term stability, ODCs based on silver catalysts are very promising for oxygen reduction in concentrated NaOH solutions. Finite-gap falling film cells appear to be the technically most mature design among the several ODC electrolysis cells that have been investigated.

Electro-organic synthesis without supporting electrolyte: Possibilities of solid polymer electrolyte technology

The application of ion exchange membranes as solid polymer electrolytes (SPE) in fuel cells is state-of-the-art. This technology needs no supporting electrolyte; consequently it can be applied for electro-organic syntheses in order to save process steps. In this case the process is not predetermined to a maximized energy efficiency so that the selection of the cell design, of the electrode materials and of the operating conditions can be focused on a high selectivity of the electrode reactions. The electro-osmotic stream, which is caused by the solvation shells of the ions during their migration through the membrane, and hence is a typical property of SPE technology, has a significant effect on the electrode reactions. It generates enhanced mass transfer at the electrodes, which is beneficial for reaction selectivity. It can be influenced by the choice of, and possibly by the preparation of, the membrane. An additional remarkable advantage of SPE technology is the exceptional long durability of oxide coated electrodes. By combination of several process engineering methods stable operation of SPE cells has been realized, even for examples of non-aqueous reaction systems. Experiments up to 6000 h duration and in cells of up to 250 cm² membrane area show the potential for industrial application.     

Longevity test results for reformate polymer electrolyte membrane fuel cell stacks

Polymer electrolyte membrane fuel cell (PEMFC) stacks offer a great potential for combined heat and power (CHP) applications because of their good performance and technical maturity of the key components. Nonetheless, some developmental issues have remained open. Among those are the long-term stability with respect to performance degradation and sudden death phenomena like membrane rupture.In a development program for domestic CHP systems, PEMFC stacks intended for long-term operation on reformate were developed. Development targets were high performance, high media utilization, good longevity and low degradation rates. In this paper, results on long-term performance tests of these stacks are reported. Operating times of more than 15,000 h with degradation rates of approx. 10 μV h⁻¹ have been achieved.     

Electrochemical detoxification of waste water without additives using solid polymer electrolyte (SPE) technology

Ion exchange membranes as solid polymer electrolytes (SPE) facilitate the electrochemical detoxification of waste water without addition of supporting electrolyte. Cation exchange membranes as H⁺ ion conductors or anion exchange membranes as OH^? ion conductors were used in combination with different electrode materials. A variety of cell configurations were investigated which differ in the direction of the electro-osmotic stream (EOS). This is a characteristical property of SPE technology, caused by the solvation shells of the ions during their migration through the membrane. Dependent on cell configuration mass transfer at the electrodes can be hindered or enhanced by EOS. In the latter case it is appropriate to increase EOS by preparation of Nafion^® membranes in order to decrease energy consumption per m³ waste water. Using a perforated membrane, which operates in this case only as ion conducting solid polymer electrolyte but not as cell separator, flow rates through the cell can be adjusted independent of the EOS and a further decrease of energy consumption is possible. The best results were obtained using anodic oxidation followed by cathodic reduction: 2-chlorophenol as example compound was destroyed almost completely and more than 80% of the chlorine was mineralized to chloride ions. By-products were detected in very low amounts, less than the remaining traces of 2-chlorophenol.     

Externally cooled high temperature polymer electrolyte membrane fuel cell stack

One key issue in high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) stack development is heat removal at the operating temperature of 140–180 °C. Conventionally, this process is done using coolants such as thermooil, steam or pressurized water. In this contribution, external liquid cooling designs are described, which are avoiding two constraints. First, in the cell active area, no liquid coolant is present avoiding any sealing problems with respect to the electrode. Secondly, the external positioning allows high temperature gradients between the heat removal zone and the active area resulting in a good adjustability of appropriate reformate conversion temperatures (e.g. 160 °C) and a more compact cell design. Different design concepts were investigated using modeling techniques and a selection of them has also been investigated experimentally. The experiments proved the feasibility of the external cooling design and showed that the temperature gradients within the active area are below 15 K under typical operating conditions.     

The behaviour of ion exchange membranes in electrolysis and electrodialysis of sodium sulphate

There is an increasing interest in the electro-chemical splitting of sodium sulphate into caustic soda solution and sulphuric acid by means of ion exchange membranes. Adaptation of the product properties to the demands of recycling requires the use of cation exchange membranes, anion exchange membranes or a combination of both. Application of available membranes results in product concentrations which are below usual industrial standards. Extensive measurements prove that the current efficiency is either dependent on concentrations of the anode region (sulphuric acid, sodium sulphate) or on the concentrations of the cathode region (caustic soda, sodium sulphate) with regard to the range of concentrations. In order to explain these phenomena a model of an acid and an alkaline state of the membrane has been developed, which can be applied both for cation and anion exchange membranes. This model is a valuable help in optimizing the concentrations of sodium sulphate, sulphuric acid and caustic soda.This paper is dedicated to Professor Dr Fritz Beck on the occasion of his 60th birthday.     

Sample comminution for mycotoxin analysis: Dry milling or slurry mixing?

A comparison was made between dry milling and slurry mixing as a comminuting step preceding mycotoxin analysis. Sample schemes of up to 30 kg are mandated by European Commission legislation. Cocoa, green coffee, almonds and pistachio samples of 10 kg were milled by a Romer analytical sampling mill and all three subsamples were analysed for aflatoxin B₁ or ochratoxin A content. The homogenization process was evaluated in terms of the analytical results, coefficients of variation for different mills and particle size distributions. Coefficients of variation for the comminuting step were higher for dry milling than for slurry mixing. This difference was explained based on measured particle size distributions for both milling types. Measurements also showed slight differences in mycotoxin content of samples based on milling procedures. This might lead to lots being wrongly accepted or rejected based on an erroneous subsample result. It was concluded that sample comminution was best performed by slurry mixing, which produced smaller particles and, consequently, homogeneous samples with lowest coefficients of variation. Additional data are given on analytical results in 10-kg subsamples that originate from the aggregate 30-kg sample as described in Commission Directive 98/53/EC.     

Influence of carbon support on the performance of platinum based oxygen reduction catalysts in a polymer electrolyte fuel cell

Novel carbons from the Sibunit family prepared via pyrolysis of hydrocarbons [Yermakov YI, Surovikin VF, Plaksin GV, Semikolenov VA, Likholobov VA, Chuvilin AL, Bogdanov SV (1987) React Kinet Catal Lett 33:435] possess a number of attractive properties for fuel cell applications. In this work Sibunit carbons with BET surface areas ranging from ca. 20 to 420 m² g⁻¹ were used as supports for platinum and the obtained catalysts were tested as cathodes in a polymer electrolyte fuel cell. The metal loading per unit surface area of carbon support was kept constant in order to maintain similar metal dispersions (∼0.3). Full cell tests revealed a strong influence of the carbon support texture on cell performance. The highest mass specific activities at 0.85 V were achieved for the 40 and 30 wt.% Pt catalysts prepared on the basis of Sibunit carbons with BET surface areas of 415 and 292 m² g⁻¹. These exceeded the mass specific activities of conventional 20 wt.% Pt/Vulcan XC-72 catalyst by a factor of ca. 4 in oxygen and 6 in air feed. Analysis of the I–U curves revealed that the improved cell performance was related to the improved mass transport in the cathode layers. The mass transport overvoltages were found to depend strongly on the specific surface area and the texture of the support.