Alcohol Fuel Cells at Optimal Temperatures

High-power-density alcohol fuel cells can relieve many of the daunting challenges facing a hydrogen energy economy. Here, such fuel cells are achieved using CsH2PO4 as the electrolyte and integrating into the anode chamber a Cu-ZnO/Al2O3 methanol steam-reforming catalyst. The temperature of operation, ~250°C, is matched both to the optimal value for fuel cell power output and for reforming. Peak power densities using methanol and ethanol were 226 and 100 mW/cm^2, respectively. The high power output (305 mW/cm^2) obtained from reformate fuel containing 1% CO demonstrates the potential of this approach with optimized reforming catalysts and also the tolerance to CO poisoning at these elevated temperatures

Polymer solid acid composite membranes for fuel-cell applications

A systematic study of the conductivity of polyvinylidene fluoride (PVDF) and CsHSO4 composites, containing 0 to 100% CsHSO4, has been carried out. The polymer, with its good mechanical properties, served as a supporting matrix for the high proton conductivity inorganic phase. The conductivity of composites exhibited a sharp increase with temperature at 142°C, characteristic of the superprotonic phase transition of CsHSO4. At high temperature (160°C), the dependence of conductivity on vol % CsHSO4 was monotonic and revealed a percolation threshold of ~10 vol %. At low temperature (100°C), a maximum in the conductivity at ~80 vol % CsHSO4 was observed. Results of preliminary fuel cell measurements are presented

Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes

The compound CsH2PO4 has emerged as a viable electrolyte for intermediate temperature (200–300 °C) fuel cells. In order to settle the question of the high temperature behavior of this material, conductivity measurements were performed by two-point AC impedance spectroscopy under humidified conditions (p[H2O] = 0.4 atm). A transition to a stable, high conductivity phase was observed at 230 °C, with the conductivity rising to a value of 2.2 × 10^–2 S cm^–1 at 240 °C and the activation energy of proton transport dropping to 0.42 eV. In the absence of active humidification, dehydration of CsH2PO4 does indeed occur, but, in contradiction to some suggestions in the literature, the dehydration process is not responsible for the high conductivity at this temperature. Electrochemical characterization by galvanostatic current interrupt (GCI) methods and three-point AC impedance spectroscopy (under uniform, humidified gases) of CsH2PO4 based fuel cells, in which a composite mixture of the electrolyte, Pt supported on carbon, Pt black and carbon black served as the electrodes, showed that the overpotential for hydrogen electrooxidation was virtually immeasurable. The overpotential for oxygen electroreduction, however, was found to be on the order of 100 mV at 100 mA cm^–2. Thus, for fuel cells in which the supported electrolyte membrane was only 25 µm in thickness and in which a peak power density of 415 mW cm^–2 was achieved, the majority of the overpotential was found to be due to the slow rate of oxygen electrocatalysis. While the much faster kinetics at the anode over those at the cathode are not surprising, the result indicates that enhancing power output beyond the present levels will require improving cathode properties rather than further lowering the electrolyte thickness. In addition to the characterization of the transport and electrochemical properties of CsH2PO4, a discussion of the entropy of the superprotonic transition and the implications for proton transport is presented

Proton conducting membrane using a solid acid

A solid acid material is used as a proton conducting membrane in an electrochemical device. The solid acid material can be one of a plurality of different kinds of materials. A binder can be added, and that binder can be either a nonconducting or a conducting binder. Nonconducting binders can be, for example, a polymer or a glass. A conducting binder enables the device to be both proton conducting and electron conducting

Solid acids as fuel cell electrolytes

Fuel cells are attractive alternatives to combustion engines for electrical power generation because of their very high efficiencies and low pollution levels. Polymer electrolyte membrane fuel cells are generally considered to be the most viable approach for mobile applications. However, these membranes require humid operating conditions, which limit the temperature of operation to less than 100°C; they are also permeable to methanol and hydrogen, which lowers fuel efficiency. Solid, inorganic, acid compounds (or simply, solid acids) such as CsHSO_4 and Rb_3H(SeO_4)_2 have been widely studied because of their high proton conductivities and phase-transition behaviour. For fuel-cell applications they offer the advantages of anhydrous proton transport and high-temperature stability (up to 250°C). Until now, however, solid acids have not been considered viable fuel-cell electrolyte alternatives owing to their solubility in water and extreme ductility at raised temperatures (above approximately 125°C). Here we show that a cell made of a CsHSO_4 electrolyte membrane (about 1.5 mm thick) operating at 150–160°C in a H_2/O_2 configuration exhibits promising electrochemical performances: open circuit voltages of 1.11 V and current densities of 44 mA cm^-2 at short circuit. Moreover, the solid-acid properties were not affected by exposure to humid atmospheres. Although these initial results show promise for applications, the use of solid acids in fuel cells will require the development of fabrication techniques to reduce electrolyte thickness, and an assessment of possible sulphur reduction following prolonged exposure to hydrogen

From Laboratory Breakthrough to Technological Realization: The Development Path for Solid Acid Fuel Cells

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Thermodynamic Analysis and Electrochemical Evaluation of CsHSO_4

A thermodynamic analysis of CsHSO₄ in oxygen and hydrogen atmospheres has been carried out. In an oxygen atmosphere, the phase relationship for the dehydration of CsHSO₄ as a function of H₂O partial pressure was established. It is concluded that CsHSO₄ is stable in a humidified oxygen atmosphere, pH₂O=0.03 atm, up to 170 °C. However, in hydrogen atmospheres, it was affirmed that CsHSO₄ is reduced to H₂S and Cs₂SO₄. Electromotive force (EMF) measurements in a humidified oxygen concentration cell, pH₂O=0.03 atm confirmed the ionic nature of the charge-carrying species. Upon thermal cycling, the voltage obtained from the high temperature phase (T=149 °C) remained unchanged for over 85 h of measurement. The volume change upon transformation to the superprotonic phase, as directly measured by high temperature X-ray powder diffraction, is +0.54%. These results demonstrate not only the stability of CsHSO₄ in oxygen but also the viability of solid acid-based electrochemical devices that would likely be subjected to thermal cycling during operation

Conductivity of potassium and rubidium dihydrogen phosphates at high temperature and pressure

The high-temperature behavior of KH₂PO₄ and RbH₂PO₄ has been investigated by several methods. Simultaneous differential scanning calorimetry and thermal gravimetry, combined with evolved gas analysis, was carried out from 25 to 500 °C under ambient pressure. The initial dehydration events in KH₂PO₄ and RbH₂PO₄ occur at 233 and 257 °C, respectively, with no indication of either solid−solid or solid−liquid transitions prior to weight loss. Application of pressure suppresses this dehydration. Impedance spectroscopy performed under 1 GPa revealed a highly reproducible superprotonic phase transition in RbH₂PO₄ at 327 °C, at which the conductivity increased several orders of magnitude to a value of 6.8 × 10⁻² Ω⁻¹ cm⁻¹ at 340 °C. The activation energy for proton transport in the superprotonic phase is ΔHₐ of 0.232 ± 0.008 eV and the pre-exponential factor A, 3.4 ± 0.6 × 10³ Ω⁻¹ cm⁻¹ K. No superprotonic solid−solid phase transition was observed in KH₂PO₄. However, a sharp increase in conductivity to a value of 1.8 × 10⁻² Ω⁻¹ cm⁻¹ at 345 °C was observed upon melting (Tm ∼ 325 °C). The liquid phase exhibited Arrhenius behavior comparable to that of superprotonic RbH₂PO₄, with ΔHₐ= 0.227 ± 0.004 eV and A = 5. 2 ± 0.5 × 10³ Ω⁻¹ cm⁻¹ K