SOLIDIONIC

Table 1. Open circuit voltage of electrochemical cells –“C(graphite) KOH·2H2O-second electrode” at 288 K

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Table 2. Electromotive forces E of «(-)M1|electrolyte|M2(+)» heterostructuresand potential U(М1) at the «М1| electrolyte» boundary relative to the referenceelectrode R at temperature Т over the entire range of temperature investigated

Fig. 3-1 Protonic heterojunction PdHx | KOH.H₂O

The special experiment to prove the reversible exchange of proton/deuteron between solid protonic conductors and Pd-electrode. The Pd membrane separate protonated-monohydrate(solid) and the liquid solution protonated also. The open circuit potential between Pd membrane and second Pd electrode (in solids) is 1100 mV after electrochemical activation. In one hours liquid solution from other side of membrane substitute for deuterated one. In the next hour because the change of isotopic composition of Pd separator it potential drop down to 1080 mV. Then we observed the strong change of potential because the change of bulk composition H/D. It is direcrt evidence in favor of protonic heterojunction.

Fig. 3-2 Electrochemical and isotopic exchange currents

Here the comparison of electrochemical exchange current through protonic heterojunction “Pd or Ti | protonics” and isotopic exchange “molecular hydrogen-protonics” is performed. The surface of protonic is flat in all cases. It seems that the rate of hydrogen species to go out/in solids is closed independently of second component of interface!!!

Fig. 3-3 Isotopic effect of cyclic voltammetry

The pair of voltammetric curves obtained at the EIS measurements of two isotopically different electrochemical cells “C(+) | KOH•2H2O | Sn (-)” and “C(+) | KOD•2D2O | Sn (-)” . Please take into account that the isotopic effect, presented on this picture, is observed without hydrogen-containing electrodes. It seems it is the pioneering finding for theoretician’s speculation.

Fig. 3-4 Self-organized micro-heterogenity of eutectic and sufficient increase on protonic conductivity?

Here you can see the very interesting phenomenon, which was revealed in the course of study the electrochemical properties of eutectics NaOH+KOH. The parent individual compound (NaOH and KOH) have conductivity sufficiently lower, than eutectic and, at least, non protonic. By our opinion such effect is due to the formation after the solidification of a micro-heterogeneity mixture of chemically different components. It is quite another situation than one at the artificially formation of composites “ionic conductor-dielectric oxide (SiO2 etc).

Fig. 3-5 Conception of corresponding states for understanding the proton mobility

In this figure self-diffusion coefficients of certain protonic conductors are presented vs reduced temperature (but reciprocal) following to conceptions of “corresponding states”. The normalized parameters has been used melting points for three compound in yellow place and the transition for copound in blue point. Let us consider more thoroughly. Unfortunately there is only two remark. First one is coincidence D(H) vs T/T* for NaOH and LiOH. Second one is parallel run of curves for eutectic and low-temperature phase of KOH.