Protonic Conductors for Intermediate Temperature Fuel Cell Electrolytes: Superprotonic CsH2PO4 Stabilization and in-Doped SnP2O7 Structure Study
Proton conductor solid electrolytes CsH2PO4 and In-doped tin pyrophosphate have been investigated as candidates to fill a gap of suitable electrolytes for fuel cells at the intermediate temperature range due their unusually high conductivities between 200 and 300 °C. Unfortunately, in the case of CsH2PO4, complicated experimental conditions, like a humidified environment, or high pressure, are needed to preserve the sought high conducting phase. In the first stage of this work, X-ray diffraction on CsH2PO 4 samples performed in air, and under normal conditions of humidity and pressure, evidence of the cubic phase of CsH2PO4 was observed during short intervals of temperature and time, starting at 215 °C and disappearing completely at 265 °C into a dehydrated phase. An AC impedance spectroscopy experimental setup has been assembled and data has been successfully collected on undoped, and doped CsH2PO 4 samples to investigate the effects of chemical and environmental modifications. Measurements performed in the temperature range 200 – 260 °C, and using the frequency range 1 – 6 MHz, showed that the high conducting phase of undoped CsH2PO4 was present for a very short interval of temperature. Additionally, these measurements showed that nano-silica-doped CsH2PO4, and CsH2PO4 under a humidified environment achieve the highest values of conductivity, above 10-2 S cm-1 among the samples tested. In the second stage of this investigation, AC impedance spectroscopy measurements were successfully performed on CsH2PO4 samples in air, at temperatures from 200 – 260 °C, and in the frequency range 1 – 6 MHz, inside a hermetically sealed stainless-steel chamber, which was designed and assembled in-house. Results showed that the highly conducting phase of CsH2PO 4 was achieved at temperatures measured above 230 °C, reaching conductivity values up to 1.7 x10-2 S cm-1, and remaining stable for over 40 hours. Consequent X-ray diffraction analysis of such samples showed that a monoclinic structure, characteristic of room temperature CsH 2PO4, was the only phase present even after the samples had been heated for over 40 hours at a temperature of 250 °C. By using this novel contraption, this has been the first time that undoped CsH2PO 4 has achieved its high conductivity phase and maintained a stable conductivity for a significant amount of time in air, without the use of a humidified environment, and without high pressure in an AC impedance spectroscopy study. Finally, in-house and synchrotron X-ray diffraction studies performed in the Sn1-xInxP2O7 series showed the cubic structure characteristic of the undoped compound at room temperature remains present up to temperatures of 250 °C. Sn0.9In 0.1P2O7, which is known to have the highest conductivity of the compound series, presented an increased unit cell as compared to the rest of the series when measured in air. However, the increased unit cell was not observed when measured under vacuum or an inert gas. Doping did not produce any major distortions on the P2O7 tetrahedra.
Martinez Salinas, Heber Jair, "Protonic Conductors for Intermediate Temperature Fuel Cell Electrolytes: Superprotonic CsH2PO4 Stabilization and in-Doped SnP2O7 Structure Study" (2017). ETD Collection for University of Texas, El Paso. AAI10620002.