Design of Block‐Copolymer Nanoporous Membranes for Robust and Safer Lithium‐Ion Battery Separators

Lithium‐ion batteries (LIBs) suffer from unsatisfied performance and safety risks mainly because of the separators. Herein, a block copolymer (BCP) composed of robust and electrolyte‐affinitive polysulfone (PSF) and Li+‐affinitive polyethylene glycol (PEG) is rationally designed to prepare a new type of LIB separator. The copolymer is subjected to selective swelling, producing nanoporous membranes with PEG chains enriched along the pore walls. Intriguingly, when used as LIB separators, thus‐produced BCP membranes efficiently integrate the merits of both PSF and PEG chains, endowing the separators thermal resistance as high as 150 °C and excellent wettability. Importantly, the nanoporous separator is able to close the pores with a temperature of 125 °C, offering the battery a thermal shutdown function. The membrane exhibits ultrahigh electrolyte uptake up to 501% and a prominent ionic conductivity of 10.1 mS cm−1 at room temperature. Batteries assembled with these membranes show excellent discharge capacity and C‐rate performance, outperforming batteries assembled from other separators including the extensively used Celgard 2400. This study demonstrates a facile strategy, selective swelling of block copolymer, to engineer high‐performance and safer LIB separators, which is also applicable to produce advanced copolymer‐based separators for other types of batteries. Selective swelling of polysulfone‐block‐polyethylene glycol leads to the production of high‐performance battery separators. Thus‐prepared separators exhibit excellent wettability, electrolyte uptake, and thermal resistance, endowing a battery with superior electrochemical performance.