Influence of Silica Nanoparticles on the Crystallization Behavior of and Proton Relaxation in Cesium Hydrogen Sulfate

The influence of nanoparticulate SiO_2 on the crystallization behavior of CsHSO_4 from aqueous solution has been quantitatively evaluated using powder X-ray diffraction (XRD) and ^1H magic angle spinning nuclear magnetic resonance (NMR) spectroscopy. It is shown that SiO_2 induces amorphization of a portion of CsHSO_4 and crystallization of the otherwise metastable phase II form of CsHSO_4. The fraction of amorphized CsHSO_4 (as determined from an evaluation of the XRD peak intensity) was found to increase from 0% in the absence of SiO_2 to fully amorphized in the presence of 90 mol % (~70 wt %) SiO_2. Within the crystalline portion of the composites, the weight fraction of CsHSO_4 phase III was observed to fall almost monotonically from 100% in the absence of SiO_2 to about 40% in the presence of 70 mol % SiO_2 (from both XRD and NMR analysis). These results suggest a crystallization pathway in which SiO_2 particles incorporate an amorphous coating of CsHSO_(4-)like material and are covered by nanoparticulate CsHSO_(4-II), which coexists with independently nucleated particles of CsHSO_(4-III). In composites with small molar fractions of CsHSO_4, the entirety of the acid salt is consumed in the amorphous region. At high CsHSO_4 content, the extent of amorphization becomes negligible, as does the extent of crystallization in metastable phase II. The phase distribution was found to be stable for over 1 year, indicating the strength of the stabilization effect that SiO_2 has on phase II of CsHSO_4

Electrochemical impedance spectroscopy of mixed conductors under a chemical potential gradient: a case study of Pt|SDC|BSCF

The AC impedance response of mixed ionic and electronic conductors (MIECs) exposed to a chemical potential gradient is derived from first principles. In such a system, the chemical potential gradient induces a gradient in the carrier concentration. For the particular system considered, 15% samarium doped ceria (SDC15) with Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2O3-) (BSCF) and Pt electrodes, the oxygen vacancy concentration is a constant under the experimental conditions and it is the electron concentration that varies. The resulting equations are mapped to an equivalent circuit that bears some resemblance to recently discussed equivalent circuit models for MIECs under uniform chemical potential conditions, but differs in that active elements, specifically, voltage-controlled current sources, occur. It is shown that from a combination of open circuit voltage measurements and AC impedance spectroscopy, it is possible to use this model to determine the oxygen partial pressure drop that occurs between the gas phase in the electrode chambers and the electrode|electrolyte interface, as well as the interfacial polarization resistance. As discussed in detail, this resistance corresponds to the slope of the interfacial polarization curve. Measurements were carried out at temperatures between 550 and 650 °C and oxygen partial pressure at the Pt anode ranging from 10^(-29) to 10^(-24) atm (attained using H_2/H_2O/Ar mixtures), while the cathode was exposed to either synthetic air or neat oxygen. The oxygen partial pressure drop at the anode was typically about five orders of magnitude, whereas that at the cathode was about 0.1 atm for measurements using air. Accordingly, the poor activity of the anode is responsible for a loss in open circuit voltage of about 0.22 V, whereas the cathode is responsible for only about 0.01 V, reflecting the high activity of BSCF for oxygen electro-reduction. The interfacial polarization resistance at the anode displayed dependences on oxygen partial pressure and on temperature that mimic those of the electronic resistivity of SDC15. This behavior is consistent with hydrogen electro-oxidation occurring directly on the ceria surface and electron migration being the rate-limiting step. However, the equivalent resistance implied by the oxygen partial pressure drop across the anode displayed slightly different behavior, possibly indicative of a more complex reaction pathway

Platinum thin film anodes for solid acid fuel cells

Hydrogen electro-oxidation kinetics at the Pt | CsH_2PO_4 interface have been evaluated. Thin films of nanocrystalline platinum 7.5–375 nm thick and 1–19 mm in diameter were sputtered atop polycrystalline discs of the proton-conducting electrolyte, CsH_2PO_4, by shadow-masking. The resulting Pt | CsH_2PO_4 | Pt symmetric cells were studied under uniform H_2-H_2O-Ar atmospheres at temperatures of 225–250 °C using AC impedance spectroscopy. For thick platinum films (>50 nm), electro-oxidation of hydrogen was found to be limited by diffusion of hydrogen through the film, whereas for thinner films, diffusion limitations are relaxed and interfacial effects become increasingly dominant. Extrapolation to vanishing film thickness implies an ultimate interfacial resistivity of 2.2 Ω cm^2, likely reflecting a process at the Pt | H_(2(g)) interface. Films 7.5 nm in thickness displayed a total electro-oxidation resistivity, R, of 3.1 Ω cm^2, approaching that of Pt-based composite anodes for solid acid fuel cells (1–2 Ω cm^2). In contrast, the Pt utilization (R^(−1)/Pt loading), 19 S mg^(−1), significantly exceeds that of composite electrodes, indicating that the thin film approach is a promising route for achieving high performance in combination with low platinum loadings

Electrochemical studies of capacitance in cerium oxide thin films and its relationship to anionic and electronic defect densities

Small polaron carrier density in epitaxial, doped CeO_2 thin films under low oxygen partial pressure was determined from electrochemically-measured capacitance after accounting for interfacial effects and shown to agree well with bulk values

Proton transport for fuel cells

No abstract

Defect chemistry of yttrium-doped barium zirconate: a thermodynamic analysis of water uptake

Thermogravimetry has been used to evaluate the equilibrium constants of the water incorporation reaction in yttrium-doped BaZrO3 with 20-40% yttrium in the temperature range 50-1000 °C under a water partial pressure of 0.023 atm. The constants, calculated under the assumption of a negligible hole concentration, were found to be linear in the Arrhenius representation only at low temperatures (≤500 °C). Nonlinearity at high temperatures is attributed to the occurrence of electronic defects. The hydration enthalpies determined here range from -22 to -26 kJ mol^-1 and are substantially smaller in magnitude than those reported previously. The difference is a direct result of the different temperature ranges employed, where previous studies have utilized higher temperature thermogravimetric measurements, despite the inapplicability of the assumption of a negligible hole concentration. The hydration entropies measured in this work, around -40 J K^-1 mol^-1, are similarly smaller in magnitude than those previously reported and are considerably smaller than what would be expected from the complete loss of entropy of vapor-phase H2O upon dissolution. This result suggests that substantial entropy is introduced into the oxide as a consequence of the hydration. The hydration reaction constants are largely independent of yttrium concentration, in agreement with earlier reports

Processing of yttrium-doped barium zirconate for high proton conductivity

The factors governing the transport properties of yttrium-doped barium zirconate (BYZ) have been explored, with the aim of attaining reproducible proton conductivity in well-densified samples. It was found that a small initial particle size (50–100 nm) and high-temperature sintering (1600 °C) in the presence of excess barium were essential. By this procedure, BaZr0.8Y0.2O3-d with 93% to 99% theoretical density and total (bulk plus grain boundary) conductivity of 7.9 × 10^-3 S/cm at 600 °C [as measured by alternating current (ac) impedance spectroscopy under humidified nitrogen] could be reliably prepared. Samples sintered in the absence of excess barium displayed yttria-like precipitates and a bulk conductivity that was reduced by more than 2 orders of magnitude

Nanoscale Electrodes by Conducting Atomic Force Microscopy: Oxygen Reduction Kinetics at the Pt|CsHSO_4 Interface

We quantitatively characterized oxygen reduction kinetics at the nanoscale Pt|CsHSO_4 interface at ~150 °C in humidified air using conducting atomic force microscopy (AFM) in conjunction with AC impedance spectroscopy and cyclic voltammetry. From the impedance measurements, oxygen reduction at Pt|CsHSO_4 was found to comprise two processes, one displaying an exponential dependence on overpotential and the other only weakly dependent on overpotential. Both interfacial processes displayed near-ideal capacitive behavior, indicating a minimal distribution in the associated relaxation time. Such a feature is taken to be characteristic of a nanoscale interface in which spatial averaging effects are absent and, furthermore, allows for the rigorous separation of multiple processes that would otherwise be convoluted in measurements using conventional macroscale electrode geometries. The complete current-voltage characteristics of the Pt|CsHSO_4 interface were measured at various points across the electrolyte surface and reveal a variation of the oxygen reduction kinetics with position. The overpotential-activated process, which dominates at voltages below -1 V, was interpreted as a charge-transfer reaction. Analysis of six different sets of Pt|CsHSO_4 experiments, within the Butler-Volmer framework, yielded exchange coefficients (α) for charge transfer ranging from 0.1 to 0.6 and exchange currents (i_0) spanning 5 orders of magnitude. The observed counter-correlation between the exchange current and exchange coefficient indicates that the extent to which the activation barrier decreases under bias (as reflected in the value of α) depends on the initial magnitude of that barrier under open circuit conditions (as reflected in the value of i_0). The clear correlation across six independent sets of measurements further indicates the suitability of conducting AFM approaches for careful and comprehensive study of electrochemical reactions at electrolyte-metal-gas boundaries

Geometrically asymmetric electrodes for probing electrochemical reaction kinetics: a case study of hydrogen at the Pt–CsH_2PO_4 interface

Electrochemical reactions can exhibit considerable asymmetry, with the polarization behavior of oxidation at a given metal|electrolyte interface differing substantially from that of reduction. The reference-less, microcontact electrode geometry, in which the electrode overpotentials are geometrically constrained to the working electrode (by limiting its area) is experimentally convenient, particularly for fuel cell studies, because the results do not rely on accurate placement of a reference electrode nor must oxidant and reductant gases be sealed off from one another. Here, the conditions under which the critical assumption of this geometry applies -— that the overpotential at the large-area counter electrode can be ignored -— is numerically assessed. It is found that, for cells of sufficiently large area, the effective radius of the counter electrode (which defines the area through which the majority of the current passes) can be expressed directly as a function of electrolyte thickness and the materials properties, σ, the conductivity of the electrolyte, and k, the reaction rate constant for the electrochemical reaction at zero-bias. From this effective radius and the true radius of the working electrode, the fraction of electrode overpotential at the latter, defined as the extent of isolation, can be readily computed. Experimental studies of hydrogen electro-oxidation/proton electro-reduction at the Pt|CsH_2PO_4 interface using two cells of differing dimensions both validate the computational results and demonstrate that asymmetry in such reactions are readily revealed in the micro-electrode, reference-less geometry. The study furthermore confirms the insensitivity of the results to the precise placement of the working electrode, while indicating the importance of very high isolation values (>99%) to ensure that overpotential contributions of the counter electrode do not influence the measurements, particularly as bias is increased