Kinetics of decomposition of the solid electrolyte RbCu4Cl3I2

The processes of electrochemical decomposition of the solid electrolyte RbCu₄Cl₃I₂ at the vitreous carbon electrode and chemical decomposition of RbCu₄Cl₃I₂ by iodine has been investigated. The anodic decomposition of the electrolyte occurs in two steps. At first, the oxidizing electrode reaction of Cu⁺ ions up to Cu²⁺ ions takes place at potentials higher than 0.57 V and onto the electrode surface the layer of decomposition products is formed, including the compound of divalent copper RbCuCl₃. Then the oxidizing reaction of I ions occurs at potentials higher than approximately 0.67 V with deposition of the iodine layer onto the electrode surface. The deposition rate of the layers of decomposition products is controlled by instantaneous nucleation and two-dimensional growth of the deposit. It was shown that slow diffusion of the iodine in the reaction product layer is a limiting step in the chemical interaction of iodine with RbCu₄Cl₃I₂. For the compressed RbCu₄Cl₃I₂ sample investigated, iodine diffusion coefficient was calculated to be 6.2×10⁻⁷ cm² s⁻¹. Iodine loss from the glassy carbon surface is about 1.1×10⁻⁴ g cm⁻² s⁻¹ at the thickness of the RbCu₄Cl₃I₂ sample is equal to 2 mm.