The solid polymer electrolytes (SPEs) fall short of the stringent requirements of solid-state lithium metal batteries, primarily due to the insufficient lithium salt dissociation and slow migration rate of Li+ ions. In this context, a composite SPE is designed by incorporating H-CN4@CN5 (C3N5 on the surface of hollow g-C3N4) heterojunction into the polyethylene oxide (PEO) matrix. Such PEO/H-CN4@CN5 significantly enhances the lithium salt dissociation by means of the spontaneous dipole moment and the built-in electric fields (BIEFs). In details, the electron depletion region of BIEFs enhances the anchoring of anions, while the electron accumulation region accelerates the rapid migration of Li+ ion. Moreover, the particular nanoflower morphology increases active sites for dissociation and transportation, while suppressing the Li dendrite growth. Hence, the Li||PEO/H-CN4@CN5||Li symmetric cell demonstrates a remarkable stability (2400 h at 0.1 mA cm−2) without lithium dendrites, and the Li||PEO/H-CN4@CN5||NCM811 batteries achieve a high-capacity density of 181.2 mAh g−1 at 0.2 C and a capacity retention of 90.5% after 100 cycles. The heterojunction filler and the innovative heterojunction structure provide a rewarding avenue towards the rational design and preparation of SPEs to build high performance rechargeable solid-state batteries.
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