To improve the safety of lithium-ion batteries (LIBs), co-polyimide (PI) P84 was introduced as a polymeric binder for Al2O3/Polymer composite surface coatings on polypropylene (PP) separators. By monitoring the dimensional shrinkage of the PP separators at high temperatures, we verified a synergistic thermal stabilization effect between the Al2O3 ceramic and the PI polymeric binder. Although PI was thermally stable up to 300 degrees C, a coating consisting solely of PI did not impede the PP separator dimensional changes (-22% at 150 degrees C). On the other hand, the Al2O3/PI-coated PP separators efficiently impeded the thermal shrinkage (-10% at 150 degrees C). In contrast, an Al2O3/poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) combination lowered the thermal stability of the PP separators (-33% at 150 degrees C). As a result, the Al2O3/PI-coated PP separators remarkably suppressed the internal short-circuit of the unit half-cells associated with separator thermal shrinkage (100 min at 160 degrees C), whereas the PVdF-HFP retained only 40 min under identical conditions. The Al2O3/PI-coated PP separators achieved rate capabilities and cell performances similar to those of the bare PP separators. (C) 2015 Elsevier B.V. All rights reserved.