Redox-active organic materials have emerged as promising alternatives to conventional inorganic electrode materials in electrochemical devices for energy storage. However, the deployment of redox-active organic materials in practical lithium-ion battery devices is hindered by their undesired solubility in electrolyte solvents, sluggish charge transfer and mass transport, as well as processing complexity. Here, we report a new molecular engineering approach to prepare redox-active polymers of intrinsic microporosity (PIMs) that possess an open network of subnanometer pores and abundant accessible carbonyl-based redox sites for fast lithium-ion transport and storage. Redox-active PIMs can be solution-processed into thin films and polymer− carbon composites with a homogeneously dispersed microstructure while remaining insoluble in electrolyte solvents. Solutionprocessed redox-active PIM electrodes demonstrate improved cycling performance in lithium-ion batteries with no apparent capacity decay. Redox-active PIMs with combined properties of intrinsic microporosity, reversible redox activity, and solution processability may have broad utility in a variety of electrochemical devices for energy storage, sensors, and electronic applications.

Redox flow batteries (RFBs) have great potential for long‐duration grid‐scale energy storage. Ion‐conducting membranes are a crucial component in RFBs, allowing charge‐carrying ions to transport while preventing the cross‐mixing of redox couples. Commercial Nafion membranes are widely used in RFBs, but their unsatisfactory ionic and molecular selectivity, as well as high costs, limit the performance and the widespread deployment of this technology. To extend the longevity and reduce the cost of RFB systems, inexpensive ion‐selective membranes that concurrently deliver low ionic resistance and high selectivity toward redox‐active species are highly desired. Here, high‐performance RFB membranes are fabricated from blends of carboxylate‐ and amidoxime‐functionalized polymers of intrinsic microporosity, which exploit the beneficial properties of both polymers. The enthalpy‐driven formation of cohesive interchain interactions, including hydrogen bonds and salt bridges, facilitates the microscopic miscibility of the blends, while ionizable functional groups within the sub‐nanometer pores allow optimization of membrane ion‐transport functions. The resulting microporous membranes demonstrate fast cation conduction with low crossover of redox‐active molecular species, enabling improved power ratings and reduced capacity fade in aqueous RFBs using anthraquinone and ferrocyanide as redox couples.

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