本论文工作通过设计新型的电解池 ,首次实现了导电聚合物的电化学现场ESR_电导同步测量 .从获得的聚苯胺ESR信号及膜电阻随电极电势变化的精细图象看出 ,极化子晶格的形成与消亡决定了聚苯胺的导电行为 .从不同电势下聚苯胺的ESR饱和行为也得到Curie自旋与Pauli自旋相互转化的新证据 .
With a new cell design, simultaneous electrochemical ESR and conductance measurements were realized for the first time. The in_situ cell consisted of a dual working electrode, a counter electrode and a reference electrode accommodated in a capillary of 1mm diameter. The dual working electrode was composed of two closely spaced Pt electrodes: a Pt disk electrode(0.5 mm diameter)sealed in a thin glass tube and a Pt layer deposited on the outside wall of the glass tube.The two working electrodes were separated by the glass gap about 20 μm thick. Two potentiostats were used to control electrode potential and maintain 10 mV potential difference between the two working electrodes. The conductivity of the polyaniline was deduced from the current passing through the polymer across the glass gap. With the new technique, an unprecedented detailed picture was obtained revealing the potential dependences of conductivity and ESR behaviors, including ESR intensity, lineshape, and saturation. Experimental results showed that the conduction mechanism could be well interpreted within the framework of the polaron lattice model. The ESR saturation data also provided a new experimental evidence for the transformation between Curie spins and Pauli spins.
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