Attempts to Electrochemically Synthesize Palladium Superhydrides By High Pressure Method – Combination of Electrolytic Hydrogen Charging and Electroplating of Protective Coatings –

Abstract

IntroductionIncited by the possibility of room-temperature superconductors in superhydrides, numerous them have been synthesized using a diamond anvil cell under high pressures up to several hundred GPa. Although palladium has widely researched for a long time as a prototype hydrogen-absorbing metal, the palladium superhydrides has not yet been obtained under such high pressures. A recent theorical calculation has predicted that the palladium superhydrides (e.g., PdH10) may be synthesized by combing electrolysis and high pressure1), but it is not certain whether it can be achieved. In this study, we attempted to synthesize the palladium superhydrides by using electrolytic hydrogen charging under high pressures, and subsequently applied protective coatings to suppress the hydrogen desorption from the palladium hydrides at ambient pressure.ExperimentalFigure shows a schematic illustration of the high-pressure apparatus. The high-pressure apparatus can apply the pressure of up to 400 MPa to the electrolyte in the electrolytic cell by pumping water into a sealed high-pressure vessel using a plunger pump and pressure multipliers. A cold-rolled palladium foil of 30 ~ 40 μm in thickness was used as a cathode, and a zinc plate was utilized as a soluble anode. Hydrogen was electrochemically loaded into the palladium foil at 0 V vs. Zn in an electrolyte consisting of 0.1 mol dm-3 sulfuric acid and 4.6 mmol dm-3 zinc sulfate under various pressures for 6 hours. Subsequently, the palladium foil was coated with the zinc film at constant current density 25 mA cm-2 for 120 seconds under the high pressure. The specimen was removed from the electrolytic cell in the high-pressure vessel at ambient pressure, and the hydrogen concentration of the palladium hydride PdH x was determined by thermal desorption spectroscopy. Structural analysis was conducted using X-ray diffraction and scanning electron microscopy.Results and discussionA number of bubbles were observed on the palladium foil surface during the electrolytic charging at ambient pressure. On the other hand, no bubbles were observed at 300 MPa. The zinc film with approximately 1.4 μm thick was coated on the PdH x surface after the electrolytic hydrogen charging. The hydrogen concentration of the PdH x was approximately x = 0.7 immediately after synthesis, which decreased to x = 0.2 without the zinc coating. On the other hand, the hydrogen concentration of the PdH x was maintained at least 1 week with the zinc coating. This result indicates that the zinc film acts as a barrier to hydrogen desorption from PdH x , and suggests that if the palladium superhydrides could be synthesized by electrolytic hydrogen charging under high pressure, it could be taken out to ambient pressure while maintaining its concentration.Reference1) W. Guan, R. J. Hemley, and V. Viswanathan, PNAS, 118, e2110470118 (2021) Figure 1