N.I. Klyui

Experimental and theoretical studies of nonlinear dependence of the internal resistance and electrode thickness for high performance supercapacitor

In this study, the internal resistance with the increasing of electrode thickness in a typical nanoporous carbon-based supercapacitor and their corresponding electrochemical performances were designed and investigated in detail. As for the carbon-based double electrode layer electrochemical system, electrochemical experiments greatly support the fact of nonlinear dependence and indicate that the curve of internal resistance vs. electrode thickness can have a minimum value when the thickness increasing from 10 to 140 μm. To explain the underlying mechanisms responsible for the nonlinear dependence, a theoretical model based on a porous electrode/electrolyte electrochemical system was proposed. As expected, the results of calculations carried out in the framework of the proposed model can be very good agreement with the experimental data. According to the calculation, the optimized electrode thickness is 53.1 μm corresponding to the minimum value of SC internal resistance. Obviously, the current research results might greatly support the nonlinear conclusion instead of linear relationship between the internal resistance and the electrode thickness and may shed some light on the fabrication and exploration of supercapacitors with high power density.

Partial Substitution of Potassium with Sodium in the K2Ti2(PO4)3 Langbeinite‐Type Framework: Synthesis and Crystalline Structure of K1.75Na0.25Ti2(PO4)3

Abstract The interaction of TiN with Na2O–K2O–P2O5 melts was investigated at (Na+K)/P molar ratios of 0.9, 1.0, and 1.2 and at Na/K molar ratios of 1.0 and 2.0. Interactions in the system led to the loss of nitrogen and the partial loss of phosphorus and resulted in the formation of KTiP2O7 and langbeinite‐type K2−xNaxTi2(PO4)3 (x=0.22–0.26) solid solutions over the temperature range of 1173 to 1053 K. The phase compositions of the obtained samples were determined by using X‐ray diffraction (including Rietveld refinement), scanning electron microscopy (using energy‐dispersive X‐ray spectroscopy and element mapping), FTIR spectroscopy, and thermogravimetric analysis/differential thermal analysis. K1.75Na0.25Ti2(PO4)3 was characterized by single‐crystal X‐ray diffraction [P213 space group, a=9.851(5) Å]. The 3D framework is built up by TiO6 octahedra and PO4 tetrahedra sharing all the oxygen vertices with the formation of cavities occupied by K(Na) cations. Only one of the two crystallographically inequivalent potassium sites is partially substituted by sodium, and this was confirmed by calculating the bond‐valence sum. The thermodynamic stability of K1.75Na0.25Ti2(PO4)3 crystals and the preferable occupation sites of NaK cationic substitutions were investigated by DFT‐based electronic structure calculations performed by the plane‐wave pseudopotential method.