Solid‐state poly(ethylene oxide) (PEO) electrolyte exhibits a low ionic conductivity at ambient conditions, and large interfacial resistance between PEO and electrodes obstructs its applications in lithium metal batteries. Heterogeneous solid electrolytes (HSEs) are an alluring solution for the exploitation of PEO. Herein, PEO/poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP)/micron‐sized Li1.4Al0.4Ti1.6(PO4)3 (LATP) heterogeneous solid electrolytes are originally prepared to decrease the crystallinity of PEO and interfacial resistance between HSEs and electrodes. Heterogeneous solid electrolyte composed of PEO/PVDF‐HFP/5% micron‐sized LATP (PPL‐5) exhibits superior electrochemical properties in ionic conductivity (3.01 × 10−5 S cm−1), lithium transference number (0.55) at 30 °C, and a broad potential window (5.31 V). Li/PPL‐5/Li symmetric cell displays a relatively stable potential response during 800 h cycling, authenticating long‐term compatibility between the as‐prepared electrolyte and lithium metal. LiFePO4 (LFP) is used as a cathode to test the chemical and electrochemical stability of PPL‐5. The discharge capacity of LFP/PPL‐5/Li coin cell maintains 97.9 mAh g−1 at 0.8 C after 500 cycles with capacity retention of 86.7%. Such excellent performance of PPL‐5 can be ascribed to the reduction of crystallinity of PEO and the improvement of the interfacial contact between electrolyte and electrodes, when PVDF‐HFP and micron‐sized LATP are simultaneously incorporated with PEO electrolyte.

Sulfur doping in carbonaceous materials is an effective approach to improve the performance of Li‐ion batteries (LIBs). Herein, sulfur‐implanted carbon dots‐embedded graphene (S‐CDs/rGO) as an anode material for LIBs is reported. A facile method is used to prepare S‐CDs/rGO by annealing the mixture of benzyl disulfide (BDS) and graphene oxide (GO). Herein, BDS serves as both the sulfur source and precursor of CDs. S‐CDs/rGO as an anode material for LIB delivers initial specific capacities of 938.8 mAh g−1 (first cycle) and 598.6 mAh g−1 (second cycle) at a current density of 100 mA g−1. S‐CDs/rGO exhibits superior cycling performance with good capacity retentions of 78.8% (500 cycles), 61.5% (2000 cycles), and 75.7% (2000 cycles) at higher current densities of 1000, 2000, and 3000 mA g−1, respectively. Moreover, the full cell assembly of the prepared S‐CDs/rGO as an anode and commercial LiFePO4 as a cathode in the voltage range of 1.5–3.9 V delivers a high reversible capacity of 203.3 mAh g−1 after extensive 1000 cycles at 500 mA g−1 with 51.8% retention (a low fading rate of 0.049% per cycle), rendering it as a promising anode material for application in high‐performance LIBs.