亚胺基团对Schiff碱基过渡金属聚合物电化学性能的影响

采用化学合成法分别制备具有不同亚胺基团的单体Ni（salen）、Ni（salphen），并分别配制成浓度为1 mmol/L单体溶液.在电化学工作站上，以制备好的碳纳米管电极片为工作电极，用循环伏安法进行电化学聚合得到对应的Schiff碱基过渡金属聚合物.用场发射扫描电镜观察聚合物的微观形貌，以及进行循环伏安法、恒流充放电法、交流阻抗谱测试.结果显示，聚合物polyNi（salen）]在碳纳米管层表面形成了带状聚合物，而聚合物polyNi（salphen）]沿着碳纳米管沉积生长.经测试得知：聚合物polyNi（salen）]和polyNi（salphen）]的最大电荷扩散系数分别为1.86×10-9 cm2/s、1.23×10-8 cm2/s,并且在0.05 mA/cm2下的比容量分别为66.6 F/g、106.3 F/g.具有亚胺苯环基团的Schiff 碱基过渡金属聚合物电化学性能较具有亚胺乙基基团的电化学性能更好.

Effects of imino groups on the electrochemical properties of transition metal complexes polymer with Schiff base

Schiff base monomer Ni (salen) and Ni (salphen) with different imino groups were chemical syn-thetized and formulated as a solution with the concentration of 1 mmol/L. PolyNi(salen)] and polyNi(salphen)] were electrodeposited on the prepared MWCNTs electrode through cyclic voltammetry on electrochemical workstation. Surface morphologies of poly Ni (salen)] and poly Ni (salphen)] electrodes were characterized by field emission scanning electron microscopy (FESEM) and electrochemical properties were test by cyclic voltammetry,chronoamperometry, galvanostatic charge/discharge methods. The results show that polyNi(salen)] nano-belts are electrodeposited upon MWCNTs, and the polyNi(salphen)] are adhesively grown on nanotubes. The charge diffusion coefficients of transition metal complexes polymer poly Ni (salen)] and poly Ni (salphen)] electrodes are 1.23×10-8 cm2/s, 1.86×10-9 cm2/s, respectively. The specific capacitances of poly Ni (salen)] and polyNi(salphen)] are 66.6 F/g、106.3 F/g at a current density of 0.05 mA/cm2, respectively. The capacitance and electrochemical properties of transition metal complexes polymer with tetradentate N2O2 Schiff-base ligand polyNi(salphen)] is better than that of polyNi(salen)].