Organic radical polymers for batteries represent some of the fastest-charging redox active materials available. Electron transport and charge storage must be accompanied by ion transport and doping for charge neutrality, but the nature of this process in organic radical polymers is not well understood. This is difficult to intuitively predict because the pendant radical group distinguishes organic radical polymers from conjugated, charged or polar polymers. Here we show for the first time a quantitative view of in situ ion transport and doping in organic radical polymers during the redox process. Two modes dominate: doping by lithium ion expulsion and doping by anion uptake. The dominance of one mode over the other is controlled by anion type, electrolyte concentration and timescale. These results apply in any scenario in which electrolyte is in contact with a non-conjugated redox active polymer and present a means of quantifying doping effects.

电池用有机自由基聚合物代表了一些充电速度最快的氧化还原活性材料。电子运输和电荷存储必须伴随着离子运输和掺杂，以实现电荷中和，但是有机自由基聚合物中该过程的性质尚未得到很好的理解。这很难直观地预测，因为侧基自由基将有机自由基聚合物与共轭，带电或极性聚合物区分开来。在这里，我们首次显示了氧化还原过程中有机自由基聚合物中原位离子迁移和掺杂的定量视图。两种模式占主导：通过锂离子排出进行掺杂和通过阴离子吸收进行掺杂。一种模式相对于另一种模式的优势受阴离子类型，电解质浓度和时间标度控制。