§Polyera Corporation, 8045 Lamon Avenue, Skokie, Illinois 60077, United States.
J Am Chem Soc. 2015 Apr 22;137(15):4956-9. doi: 10.1021/jacs.5b02290. Epub 2015 Apr 11.
We report here the first successful demonstration of a "π-conjugated redox polymer" simultaneously featuring a π-conjugated backbone and integrated redox sites, which can be stably and reversibly n-doped to a high doping level of 2.0 with significantly enhanced electronic conductivity. The properties of such a heavily n-dopable polymer, poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2)), were compared vis-à-vis to those of the corresponding backbone-insulated poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5'-[2,2'-(1,2-ethanediyl)bithiophene]} (P(NDI2OD-TET)). When evaluated as a charge storage material for rechargeable Li batteries, P(NDI2OD-T2) delivers 95% of its theoretical capacity at a high rate of 100C (72 s per charge-discharge cycle) under practical measurement conditions as well as 96% capacity retention after 3000 cycles of deep discharge-charge. Electrochemical, impedance, and charge-transport measurements unambiguously demonstrate that the ultrafast electrode kinetics of P(NDI2OD-T2) are attributed to the high electronic conductivity of the polymer in the heavily n-doped state.
我们首次成功展示了一种同时具有共轭主链和集成氧化还原位点的“π 共轭氧化还原聚合物”，它可以稳定且可逆地被 n 掺杂至高掺杂水平 2.0，同时显著提高电子电导率。这种可高度 n 掺杂聚合物的性质，聚{[N,N'-双（2-辛基十二烷基）-1,4,5,8-萘二羧酸二酰亚胺-2,6-二基]-交替-5,5'-(2,2'-联噻吩)}（P（NDI2OD-T2））与相应的主链隔离聚合物聚{[N,N'-双（2-辛基十二烷基）-1,4,5,8-萘二羧酸二酰亚胺-2,6-二基]-交替-5,5'-[2,2'-(1,2-乙二基)联噻吩]}（P（NDI2OD-TET））进行了比较。当用作可再充电 Li 电池的电荷存储材料时，P（NDI2OD-T2）在实际测量条件下以 100C 的高倍率（每个充放电循环 72 秒）可达到其理论容量的 95%，并且在深度放电-充电 3000 次循环后仍保持 96%的容量保持率。电化学、阻抗和电荷传输测量清楚地表明，P（NDI2OD-T2）的超快电极动力学归因于聚合物在高掺杂状态下的高电子电导率。
