The irreversible interfacial side reactions of lithium-rich layered oxides at high voltage lead to deterioration of cycling performance. Herein, we construct a Ce³⁺-rich surface layer on the lithium-rich layered oxides surface. Owing to the strong chemical affinity between rare-earth elements and oxygen, the Ce-rich spinel surface layer is completely encapsulated around the lithium-rich layered oxides particles. Also, an excess of Ce³⁺ leads to the formation of Li_xCeO_2−y nanoparticles, which are adorned on the surface layer. This surface modification lowers the work function, promoting the formation of a thin, inorganic-rich, and uniform cathode–electrolyte interphase. Consequently, this layer mitigates the dissolution of transition metals and enhances the stability of the surface lattice oxygen. Consequently, the LLO@Ce cathode demonstrates a high-capacity retention of 93.12% at 1 C after 500 cycles. This work presents a promising path for stabilizing the surface of lithium-rich layered oxides, thereby enhancing its cycling performance for high-energy-density lithium-ion batteries.

Organic electrode materials (OEMs) constitute an attractive class of energy storage materials for potassium-ion batteries, but their application is severely hindered by sluggish kinetics and limited capacities. Herein, inorganic molecules covalent combination strategy is proposed to drive advanced potassium organic batteries. Specifically, molecular selenium, possessing high potential of conductivity and electroactivity, is covalently bonded with organic matrix, that is symmetrical selenophene-annulated dipolyperylene diimide (PDI2-2Se), is designed to verify the feasibility. The inorganic-anchored OEM (PDI2-2Se) can be electrochemically activated to form organic (PDI2 matrix)–inorganic (Se) hybrids during initial cycles. Stateof-the-art 3D tomography reveals that a “mutual-accelerating” effect was realized, that is, the 10-nm Se quantum dots, possessing high conductivity, facilitate charge transfer in organics as well store K⁺-ions, and organic PDI2 matrix benefits the encapsulation of Se, thereby suppressing shuttle effect and volume fluctuation during cycling, endowing resulting PDI2/Se hybrids with both high-rate capacities and longevity. The concept of inorganicconfigurated OEM through covalent bonds, in principle, can also be extended to design novel functional organic-redox electrodes for other high-performance secondary batteries.