I-60 Influence of metal coordination on conductivity behavior in poly(butadiene-acrylonitrile)-CoCl2 system [Text] / O. V. Bushkova, I. P. Koryakova, Yu. A. Skorik, B.I. Lirova, A. V. Pestov, V. M. Zhukovskii // Electrochimica Acta. - 2008. - Vol. 53, № 16. - P5322-5333 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: The metal complex formation and the electrical properties of amorphous solid polymer electrolytes, based on poly(butadiene-acrylonitrile) copolymer (PBAN) and CoCl2, have been studied over the homogeneity region of the system limited by the CoCl2 concentration of 1.89 mol kg-1. It has been found that ionic conductivity is carried out by the unipolar anion transfer at lower CoCl2 concentrations (up to 0.10 mol kg-1). As the CoCl2 concentration increases, electronic conductivity appears in addition to ionic conductivity, and the former becomes dominant, starting from 0.38 mol kg-1. It has been shown that the nature of charge carriers is determined by the composition of metal complexes formed by CoCl2 and the macromolecular solvent PBAN. At lower concentrations, the [Co2L2Cl4]0 dimers are the predominant species (L being macromolecule side groups C{triple bond, long}N), and their dissociation is followed by the formation of mobile Cl- anions and immobile binuclear [Co2Cl3]+ complexes. As CoCl2 concentration increases, polynuclear [ConL2Cl2n]0 (n 2) complexes appear (L being C{triple bond, long}N and C{double bond, long}C groups of PBAN). Specific features of chemical bonds in ?-complexes of transition metals result in the appearance of electronic charge carriers. The abrupt increase in conductivity observed at the highest CoCl2 concentration is connected with the formation of a percolation network of polynuclear [ConL2Cl2n]0 complexes |