A closer look at superionic phase transition in (NH₄)₄H₂(SeO₄)₃: impedance spectroscopy under pressure

Abstract

The proton-conducting material (NH 4 ) 4 H 2 (SeO 4 ) 3 is examined to check whether its conductivity spectra are sensitive to subtle changes in the crystal structure and proton dynamics caused by external pressure. The AC conductivity was measured using impedance spectroscopy, in the frequency range from 100 Hz to 1 MHz, at temperatures 260 K < T < 400 K and pressures 0.1 MPa < p < 500 MPa. On the basis of the impedance spectra, carefully analyzed at different thermodynamic conditions, the p-T phase diagram of the crystal is constructed. It is found to be linear in the pressure range of the experiment, with the pressure coefficient value dT s /dp = À0.023 K MPa À1 . The hydrostatic pressure effect on proton conductivity is also presented and discussed. Measurements of the electrical conductivity versus time were performed at a selected temperature T = 352.3 K and at pressures 0.1 MPa < p < 360 MPa. At fixed thermodynamic conditions (p = 302 MPa, T = 352.3 K), the sluggish solid-solid transformation from low conducting to superionic phase was induced. It is established that the kinetics of this transformation can be described by the Avrami model with an effective Avrami index value of about 4, which corresponds to the classical value associated with the homogeneous nucleation and three-dimensional growth of a new phase.

A Closer Look at Structural Relaxation in Superionic (NH4)4H2(SeO4)3: 1H NMR Studies

“…In our previous paper, on the kinetics of the superionic transition in TeAHSe, we emphasized the critical role of NH 4 + cations and their N−H•••O subnetwork of hydrogen bonds in the structure stabilization process of this crystal. 11 The present study is aimed at determination of the role of NH 4…”