Merinda, LaurienLaurienMerindaYuwono, Rio AkbarRio AkbarYuwonoWang, Fu-MingFu-MingWangNAE-LIH WUSundari, Citra Deliana DewiCitra Deliana DewiSundariKhotimah, ChusnulChusnulKhotimahHsieh, Han-PinHan-PinHsiehChang, Jeng-KueiJeng-KueiChangHaw, Shu-ChihShu-ChihHawPao, Chih-WenChih-WenPaoChen, Jeng-LungJeng-LungChenXu, QunjieQunjieXuWu, YunwenYunwenWuChen, Chi-LiangChi-LiangChenChan, Ting-ShanTing-ShanChan2025-12-182025-12-182025-12-0113858947https://www.scopus.com/record/display.uri?eid=2-s2.0-105021602466&origin=resultslisthttps://scholars.lib.ntu.edu.tw/handle/123456789/734752LiNi0.8Mn0.1Co0.1O2 (NMC811) exceeding a high specific discharge capacity of 200 mAh g−1. However, this cathode, distinct parasitic reactions with electrolyte are induced by the nucleophilic site on its surface. Here, electron-withdrawing cis-isomerism oligomers are synthesized from phenylenedimaleimide positional isomers to prevent these parasitic reactions. The para and meta substituent oligomerize through a vinyl radical mechanism, which is followed by the C-OH formation. Meanwhile, the oligomerization of ortho substituent (o-OC) gives a more electron-withdrawing carbonyl functional group due to the propagation radical polymerization pathway. This electron-withdrawing group increases the hybridization of Ni[sbnd]O according to soft X-ray absorption spectroscopy to further catalyze the polymerization of the oligomer as an artificial cathode electrolyte interphase. Interestingly, due to a smaller angular distance (~60°) between the two maleimide groups of o-CI, leading to the formation of porous organic coverage on NCM811. These unique properties of o-CI and its interaction with NCM811 lead to the entropy-driven ethylene carbonate (EC) to vinylene carbonate (VC) reaction through a direct second deprotonation mechanism. Consequently, the cycle stability is enhanced compared to pristine NCM811 after prolonged cycling. This work demonstrates a coating layer strategy to grant a beneficial conversing of EC to VC.falseCoverageElectrolyte decompositionLithium-ion batteryLocalized entropy drivenNi-rich compoundOne-step deprotonationjournal article10.1016/j.cej.2025.1707032-s2.0-105021602466