Multifunctional self-reconstructive cathode/electrolyte interphase layer for cobalt-free Li-rich layered oxide cathode

•This work resolves the typical issues induced by the collaboration failure mechanism at the interface between lithium-rich cathode and electrolyte.•A multifunctional self-reconstructive CEI layer with active oxygen/water scavenging capability is designed to modify mechanical/electrochemical stability.•This additive-induced self-reconstructive CEI layer design endows the lithium-rich cathode with superior cycling performance at both half and full cells.•This work establishes guidelines for designing a self-reconstructive CEI layer to decrease undesired collaboration failure mechanisms in lithium-rich cathode systems.