ELECTROCHEMICAL APPLICATIONS OF THE BENDING BEAM METHOD .1. MASS-TRANSPORT AND VOLUME CHANGES IN POLYPYRROLE DURING REDOX
ELECTROCHEMICAL APPLICATIONS OF THE BENDING BEAM METHOD .1. MASS-TRANSPORT AND VOLUME CHANGES IN POLYPYRROLE DURING REDOX
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DOI：
10.1021/j100204a071
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发表时间：
1992-12-10
影响因子：
--
通讯作者：
INGANAS, O
中科院分区：
文献类型：
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作者：
PEI, QB;INGANAS, O
我们将弯曲束方法引入到聚吡咯(PPy)电极的电化学研究中，其中由PPy层和聚乙烯层结合在一起的双聚合物条通过弯曲响应于PPy层在电化学掺杂和非掺杂过程中的体积变化。建立了局部线应变与带材曲率变化之间的关系式。当在LiClO4水溶液中还原(不掺杂)时，对甲苯磺酸盐掺杂的PPy经历了最初的快速膨胀和随后的快速收缩和持续的缓慢收缩。体积变化在0.65-3.4%的范围内。提出并用循环伏安法证实了电荷补偿溶液中的阳离子插入控制了非掺杂的净速率、盐(对甲苯磺酸钠)在零电流下从还原的中性PP0中排出以及排出盐后PPy0中的相松弛。阳离子插入较快，D(Li)约为10(-7)cm~2·S~(-1)，排盐较慢，D(S)约为10(-9)cm~2·S~(-1)，具体取决于聚吡咯层的厚度。给出了阳离子插入、放盐和弯曲行为的数学模型，并与实验结果进行了比较。
We introduce the bending beam method to studies of the electrochemistry of polypyrrole (PPy) electrodes, where a bipolymer strip made of a PPy layer and a polyethylene layer bound together responds, by bending, to volume changes in the PPy layer during its electrochemical doping and undoping. A correlation between the local linear strain and the curvature change of the strip is developed. Upon reduction (undoping) in an aqueous solution of LiClO4, a tosylate-doped PPy undergoes initial rapid swelling and subsequent rapid shrinking and continuous slow shrinking. The volume changes are in the range 0.65-3.4%. Cation insertion from the solution for charge compensation, which controls the net rate of the undoping, salt (sodium tosylate) draining out of the reduced neutral PPy0 at zero current, and phase relaxation in the PPy0 after salt draining are proposed and confirmed by cyclic voltammetry. The cation insertion is fast with D(Li) around 10(-7) cm2 s-1, and salt draining is slow with D(s) around 10(-9) cm2 s-1, depending on the thickness of the PPy layer. Mathematical models of the cation insertion, salt draining, and bending behavior are given and compared with the experimental results.