The Influence of Water on the Cycling Behavior of the Polypyrrole Electrode in Lithium Cells

Two different types of polypyrrole (PPy) have been synthesized: the dry form from 0.2{ital M} pyrrole (Py) + 0.5{ital M} LiClO{sub 4} propylene carbonate (PC) and the wet one from 0.2{ital M} Py + 0.56{ital M} H{sub 2}O + 0.5{ital M} LiClO{sub 4} in PC. The polymerization of pyrrole in both electrolytes starts at + 3.46 V ({ital vs}. Li/Li{sup +}) and follows nearly the same {ital E-I} curve. During the first discharge clear differences in electrochemical behavior can already be seen. During the first 1,000 cycles performed on 1-{mu}m thin PPy layers in the dry 0.5{ital M} LiClO{sub 4} (PC) electrolyte, the coulombic capacity of the dry form of PPy dropped to about 80% of its initial value. The cycling behavior of the wet form is even better---the doping level is slightly higher and the capacity drops to 80% of its initial value after more than 20,000 cycles, when cycled in the optimum potential interval from 2.0 to 4.0 V ({ital vs}. Li/Li{sup +}). Cyclic voltammograms and {ital in situ} FTIR measurements revealed that there is a gradual, slight loss of the most negative redox sites with increasing cycle number, accompanied by an increase in the amount of themore » irreversibly (over)oxidized PPy found in the neutral form of the polymer. The self-discharge loss on {approx} 50-{mu}m-thick PPy foils was found to be about 1% per day.« less